WO2020066770A1 - Nitrile rubber composition and method for producing nitrile rubber composition - Google Patents
Nitrile rubber composition and method for producing nitrile rubber composition Download PDFInfo
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- WO2020066770A1 WO2020066770A1 PCT/JP2019/036482 JP2019036482W WO2020066770A1 WO 2020066770 A1 WO2020066770 A1 WO 2020066770A1 JP 2019036482 W JP2019036482 W JP 2019036482W WO 2020066770 A1 WO2020066770 A1 WO 2020066770A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
Definitions
- the present invention provides a nitrile rubber composition which is excellent in processability, and can provide a rubber crosslinked product having excellent compression set resistance, compression stress retention and cold resistance, and a nitrile rubber composition such as this.
- the present invention relates to a crosslinkable nitrile rubber composition and a crosslinked rubber obtained by using the composition.
- the invention also relates to a method for producing such a nitrile rubber composition.
- rubbers containing an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit and a conjugated diene monomer unit are known as rubbers having excellent fuel oil resistance. It is mainly used as a material for rubber products around various oils of automobiles such as fuel hoses, gaskets, packings, oil seals and the like.
- nitrile group-containing copolymer is required. It is effective to increase the amount of the nitrile group-containing monomer in the combined rubber and to hydrogenate the nitrile group-containing copolymer rubber. However, when the amount of the nitrile group-containing monomer in the nitrile group-containing copolymer rubber is increased or when hydrogenated, it becomes hard when blended with a vinyl chloride resin, resulting in reduced workability. was there.
- ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units were used as a nitrile group-containing copolymer rubber in order to further improve fuel oil resistance and heat resistance.
- a rubber crosslinked product obtained by using such a rubber composition has a compression set resistance, a compression stress
- the inventors have found that they have excellent retention and cold resistance, and have completed the present invention.
- a nitrile group-containing copolymer rubber (A) containing ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units at a ratio of 40 to 50% by weight and an iodine value of 5 to 50 is used.
- a plasticizer (C) having a molecular weight of 500 to 2,000.
- the plasticizer (C) is preferably a polyetherester (c1) represented by the following general formula (1).
- R 1 is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
- R 2 is each independently a hydrogen atom or a 1 to 6 carbon atom.
- n is an integer of 1 to 40.
- the plasticizer (C) is preferably an adipic acid-based polyester (c2) having a molecular weight of 800 to 2,000 and a viscosity at 25 ° C. of 50 to 1500 mPa ⁇ s. .
- the content of the plasticizer (C) is preferably 1 to 60 parts by weight based on 100 parts by weight of the nitrile group-containing copolymer rubber (A).
- a crosslinkable nitrile rubber composition comprising the above nitrile rubber composition of the present invention and a crosslinking agent. Further, according to the present invention, there is provided a cross-linked rubber obtained by cross-linking the cross-linkable nitrile rubber composition of the present invention.
- a nitrile group-containing copolymer rubber (A) containing an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit at a ratio of 40 to 50% by weight and an iodine value of 5 to 50 is used.
- a vinyl chloride resin (B), a plasticizer (C) having a molecular weight of 500 to 2,000, and a compounding agent the method comprising producing a nitrile rubber composition, First mixing in which a part of the total amount of the plasticizer (C) to be contained in the nitrile rubber composition is mixed with the nitrile group-containing copolymer rubber (A) and the vinyl chloride resin (B).
- a second mixing step in which the composition obtained in the first mixing step is mixed with the rest of the total amount of the plasticizer (C) to be contained in the nitrile rubber composition and the compounding agent, and a second mixing step is performed.
- a method for producing a nitrile rubber composition comprising:
- the blending amount of the plasticizer (C) in the first mixing step is 10% of the total amount of the plasticizer (C) contained in the nitrile rubber composition. It is preferable to set it to 90% by weight.
- the compounding agent preferably contains at least a filler.
- a nitrile rubber composition which is excellent in processability and can give a rubber crosslinked product having excellent compression set resistance, compression stress retention and cold resistance. Further, according to the present invention, there is provided a crosslinkable nitrile rubber composition and a rubber crosslinked product obtained by using such a nitrile rubber composition, and a method for producing such a nitrile rubber composition. Can also.
- the nitrile rubber composition of the present invention contains a nitrile group-containing copolymer rubber containing an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit at a ratio of 40 to 50% by weight and an iodine value of 5 to 50 ( A), a vinyl chloride resin (B), and a plasticizer (C) having a molecular weight of 500 to 2,000.
- the nitrile group-containing copolymer rubber (A) used in the present invention contains an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit in a proportion of 40 to 50% by weight, and has an iodine value in a range of 5 to 50. There is something.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer which forms the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit contained in the nitrile group-containing copolymer rubber (A) used in the present invention is: There is no particular limitation, and acrylonitrile; ⁇ -halogenoacrylonitrile such as ⁇ -chloroacrylonitrile and ⁇ -bromoacrylonitrile; ⁇ -alkylacrylonitrile such as methacrylonitrile and ethacrylonitrile; Among these, acrylonitrile and methacrylonitrile are preferred, and acrylonitrile is particularly preferred.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer may be used alone or in combination of two or more.
- the content of ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units in the nitrile group-containing copolymer rubber (A) used in the present invention is 40 to 50% by weight based on all monomer units. And preferably 42 to 50% by weight, more preferably 44 to 50% by weight, still more preferably 44 to 49% by weight, and still more preferably 44 to 48% by weight.
- the obtained cross-linked rubber can have excellent fuel oil resistance.
- the obtained rubber cross-linked product may be inferior in fuel oil resistance, while if too large, the cold resistance may be reduced. There is.
- ⁇ , ⁇ -ethylenically unsaturated nitrile in the entire mixture of rubbers having different monomer compositions is used.
- the content ratio of the monomer unit may be within the above range (the same applies to a copolymerizable monomer unit including a diene monomer unit and / or an ⁇ -olefin monomer unit described later).
- the nitrile group-containing copolymer rubber of the present invention preferably further contains a diene monomer unit and / or an ⁇ -olefin monomer unit from the viewpoint of improving mechanical properties due to rubber elasticity. .
- Examples of the diene monomer forming the diene monomer unit include conjugated dienes having 4 or more carbon atoms, such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene.
- conjugated dienes having 5 to 12 carbon atoms such as 1,4-pentadiene and 1,4-hexadiene; Of these, conjugated dienes are preferred, and 1,3-butadiene is more preferred.
- the ⁇ -olefin monomer forming the ⁇ -olefin monomer unit preferably has 2 to 12 carbon atoms and includes ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1- Hexene, 1-octene and the like are exemplified.
- One of these diene monomers and ⁇ -olefin monomers may be used alone, or two or more thereof may be used in combination.
- the lower limit of the content of the diene monomer unit and / or the ⁇ -olefin monomer unit is based on all monomer units. It is preferably at least 40% by weight, more preferably at least 50% by weight, still more preferably at least 51% by weight, still more preferably at least 52% by weight, and the upper limit thereof is preferably at most 60% by weight, more preferably at least 58% by weight. %, More preferably 56% by weight or less.
- the nitrile group-containing copolymer rubber (A) used in the present invention may contain, in addition to the above ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit, a diene monomer unit and an ⁇ -olefin monomer unit, It may contain units of other monomers copolymerizable with the monomers forming these monomer units.
- the content ratio of such another monomer unit is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less, based on all monomer units.
- Such other copolymerizable monomers include, for example, aromatic vinyl compounds such as styrene, ⁇ -methylstyrene and vinyltoluene; fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethylstyrene, pentafluoro Fluorine-containing vinyl compounds such as vinyl benzoate, difluoroethylene and tetrafluoroethylene; ⁇ -olefin compounds such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene; acrylic acid; ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids such as methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, fumaric anhydride and anhydrides thereof; methyl (meth) acrylate, (meth) ) Ethyl acrylate, (
- the nitrile group-containing copolymer rubber (A) used in the present invention has an iodine value of 5 to 50, preferably 8 to 45, more preferably 10 to 40, and still more preferably 18 to 30. If the iodine value of the nitrile group-containing copolymer rubber (A) is too high, the heat resistance and ozone resistance of the obtained rubber cross-linked product may be reduced, and if the iodine value is too low, the obtained rubber cross-linked product Mechanical properties may be reduced.
- the cross-linking agent when a sulfur-based cross-linking agent is used as the cross-linking agent, by setting the iodine value within the above range, vulcanization can be made good and appropriate, so that the obtained rubber cross-linked product is excellent. While maintaining excellent heat resistance, it is possible to obtain more excellent compression set resistance and compression stress retention.
- the iodine value of the entire mixture of rubbers having different iodine values may be within the above range.
- the polymer Mooney viscosity (ML1 + 4, 100 ° C.) of the nitrile group-containing copolymer rubber (A) used in the present invention is preferably 10 to 200, more preferably 15 to 150, and still more preferably 15 to 100.
- nitrile group-containing copolymer rubber (A) one kind of rubber may be used, or two or more kinds of rubbers may be used in combination. It suffices that the average value of these characteristic values (the average value of the characteristic values taking into account the amount used) be within the above range, but the characteristic value of each of the two or more rubbers used is , Preferably within the above range.
- the method for producing the nitrile group-containing copolymer rubber (A) used in the present invention is not particularly limited, but the above-mentioned monomers are copolymerized, and if necessary, the carbon-carbon dimer in the resulting copolymer is obtained. It can be produced by hydrogenating a heavy bond.
- the polymerization method is not particularly limited, and may be a known emulsion polymerization method or a solution polymerization method. From the viewpoint of industrial productivity, the emulsion polymerization method is preferable.
- a commonly used polymerization auxiliary material can be used in addition to the emulsifier, the polymerization initiator, and the molecular weight modifier.
- the vinyl chloride resin (B) used in the present invention may be any one as long as the main constituent monomer constituting the resin is vinyl chloride, and the content of the vinyl chloride monomer unit is 50 to 100% by weight. Preferably, it is 60 to 100% by weight, more preferably 70 to 100% by weight.
- the obtained rubber crosslinked product can be excellent in ozone resistance, fuel oil swelling resistance, and fuel oil permeability.
- the degree of polymerization of the vinyl chloride resin (B) is not particularly limited, but the average degree of polymerization measured by a solution viscosity method prescribed in JIS K6720-2: 1999 is preferably 400 to 3000, more preferably 600 to 2000. .
- the average degree of polymerization is in the above range, the ozone resistance, fuel oil swelling resistance, and fuel oil permeability of the obtained rubber cross-linked product are further improved while improving the processability of the nitrile rubber composition. Can be.
- the content of the vinyl chloride resin (B) in the nitrile rubber composition of the present invention is preferably 5 to 120 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the nitrile group-containing copolymer rubber (A).
- the amount is 110 parts by weight, more preferably 20 to 100 parts by weight, still more preferably 25 to 80 parts by weight, particularly preferably 40 to 70 parts by weight.
- the nitrile rubber composition of the present invention contains a plasticizer (C) having a molecular weight of 500 to 2,000 in addition to the nitrile group-containing copolymer rubber (A) and the vinyl chloride resin (B).
- the plasticizer (C) having a molecular weight of 500 to 2,000 (hereinafter, appropriately referred to as “plasticizer (C)”) is used as the above-mentioned nitrile group-containing copolymer rubber (A) and vinyl chloride resin (B).
- the nitrile rubber composition can have excellent workability, and furthermore, the obtained rubber
- the crosslinked product can be made excellent in compression set resistance, compression stress retention and cold resistance.
- the above-mentioned nitrile group-containing copolymer rubber (A) and vinyl chloride resin (B) are used, the effects derived from them, that is, the obtained rubber cross-linked product is used as a fuel-resistant oil It also has the effect of being able to have excellent swelling properties, fuel oil permeability, ozone resistance and heat resistance.
- the obtained rubber cross-linked product in addition to compression set resistance, can also be excellent in compressive stress retention, so that it can be used for compression, particularly for metal-bonded parts. It can be suitably used for fuel hose applications having a crimped portion with a rubber crosslinked product.
- the plasticizer (C) is not particularly limited as long as it has a molecular weight in the range of 500 to 2,000. From the viewpoint that the obtained rubber cross-linked product can further increase the compressive stress retention, the polyetherester (c1) represented by the formula (1) or the adipic acid-based polyester (c2) having a molecular weight of 800 to 2,000 and a viscosity at 25 ° C. of 50 to 1500 mPa ⁇ s is preferable.
- R 1 is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms. Particularly preferred is a hydrocarbon group having 1 to 10 carbon atoms.
- R 2 is each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms. And more preferably a hydrogen atom.
- n is an integer of 1 to 40, preferably an integer of 2 to 30, and more preferably an integer of 3 to 30.
- polyetherester (c1) represented by the general formula (1) for example, a corresponding alkylene oxide polymer is obtained, and a terminal hydroxyl group of the obtained polymer is reacted with a corresponding carboxylic acid. Thus, it can be produced by esterification.
- the molecular weight of the polyetherester (c1) represented by the general formula (1) is in the range of 500 to 1200 from the viewpoint that the obtained rubber crosslinked product can have a higher compressive stress retention. Those having a molecular weight in the range of 520 to 900 are more preferable.
- the polyetherester (c1) represented by the general formula (1) has a viscosity at a temperature of 25 ° C. Those in the range of 15 to 300 mPa ⁇ s are preferable, those in the range of 22 to 150 mPa ⁇ s are more preferable, and those in the range of 25 to 100 mPa ⁇ s are particularly preferable.
- polyetherester (c1) represented by the general formula (1) those having a flash point in the range of 216 to 300 ° C. are preferable, and those having a flash point in the range of 220 to 260 ° C. are more preferable. preferable.
- an adipic acid-based polyester (c2) having a molecular weight of 800 to 2,000 and a viscosity at a temperature of 25 ° C. of 50 to 1500 mPa ⁇ s (hereinafter referred to as “adipic acid-based polyester (c2 ) ”) Is also preferably used.
- adipic acid-based polyester (c2) a reaction product of an adipic acid, which is a dicarboxylic acid, and an alcohol having a molecular weight and a viscosity at a temperature of 25 ° C. within the above ranges is used. There is no particular limitation as long as it exists.
- the adipic acid-based polyester (c2) is, for example, a reaction product of adipic acid and a polyhydric alcohol, or a product obtained by further reacting a monohydric alcohol or a monocarboxylic acid in addition to adipic acid and a polyhydric alcohol. You may.
- Examples of the dihydric alcohol include ethylene glycol, propylene glycol, butanediol, 1.6-hexanediol and the like.
- Examples of the monohydric alcohol include nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, hexadecanol, octadecanol and the like.
- Examples of the monovalent carboxylic acid include nonanoic acid, capric acid, undecylic acid, and lauric acid.
- the adipic acid-based polyester (c2) may be any polyester having a molecular weight of 800 to 2,000 and a viscosity at a temperature of 25 ° C. of 50 to 1500 mPa ⁇ s. From the viewpoint that the molecular weight can be increased, those having a molecular weight in the range of 900 to 1600 are preferable, and those having a molecular weight in the range of 1000 to 1300 are more preferable. Further, from the viewpoint that the obtained rubber cross-linked product can further increase the compressive stress retention, the viscosity at a temperature of 25 ° C. is preferably in the range of 500 to 1200 mPa ⁇ s, and more preferably in the range of 650 to 1000 mPa ⁇ s.
- adipic acid-based polyester (c2) those having a flash point in the range of 216 to 300 ° C. are preferable, and those having a flash point in the range of 220 to 260 ° C. are more preferable.
- plasticizer (C) one type may be used alone, or two or more types may be used in combination.
- plasticizer (C) two or more kinds of polyetheresters (c1) represented by the above general formula (1) may be used, or two or more kinds may be used.
- the adipic acid-based polyester (c2) may be used, or a combination of the polyetherester (c1) represented by the general formula (1) and the adipic acid-based polyester (c2) may be used. .
- the content of the plasticizer (C) in the nitrile rubber composition of the present invention is preferably 1 to 60 parts by weight, more preferably 3 to 55 parts by weight, based on 100 parts by weight of the nitrile group-containing copolymer rubber (A). Parts by weight, more preferably 5 to 50 parts by weight, even more preferably 8 to 40 parts by weight, particularly preferably 10 to 40 parts by weight, most preferably 15 to 30 parts by weight.
- the nitrile rubber composition of the present invention preferably further contains a stabilizer.
- the stabilizer may be any compound that acts as a stabilizer for the vinyl chloride resin, and is not particularly limited.
- Calcium-zinc stabilizer, calcium-magnesium-zinc stabilizer, barium-zinc stabilizer, tin-based stabilizer Examples include stabilizers, lead stabilizers, hydrotalcite stabilizers, and zeolite stabilizers. Of these, calcium-magnesium-zinc stabilizers and hydrotalcite stabilizers are preferred. Magnesium-zinc stabilizers are more preferred.
- the content of the stabilizer in the nitrile rubber composition of the present invention is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts by weight, further preferably 5 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin (B). 4545 parts by weight.
- the nitrile rubber composition of the present invention may contain various compounding agents used in the rubber field.
- a compounding agent typically includes a filler.
- Fillers include ⁇ , ⁇ -ethylenic substances such as carbon black, silica, calcium carbonate, aluminum silicate, magnesium silicate, calcium silicate, magnesium oxide, short fibers, zinc (meth) acrylate and magnesium (meth) acrylate. And unsaturated carboxylic acid metal salts. Among them, carbon black and silica are preferred, and carbon black is more preferred, from the viewpoint that the mechanical strength can be further increased.
- the filler a filler whose surface is surface-treated with a surface treatment agent or the like may be used.
- Carbon black is not particularly limited, but examples thereof include furnace black, acetylene black, thermal black, channel black, and graphite.
- furnace black is preferably used, and specific examples thereof include SAF, ISAF, ISAF-HS, ISAF-LS, HAF, HAF-HS, HAF-LS, FEF, SRF, FT, and MT. No. These may be used alone or in combination of two or more.
- Silica is not particularly limited, but for example, dry-process white carbon, wet-process white carbon, colloidal silica, precipitated silica, surface-treated silica, and the like can be used. Alternatively, a carbon-silica dual phase filler having silica supported on the surface of carbon black may be used.
- the content of the filler in the nitrile rubber composition of the present invention is preferably 10 to 80 parts by weight, more preferably 15 to 75 parts by weight, based on 100 parts by weight of the nitrile group-containing copolymer rubber (A). More preferably, the amount is 20 to 70 parts by weight.
- the nitrile rubber composition of the present invention preferably further contains a cross-linking agent.
- a cross-linking agent By adding a cross-linking agent, the nitrile rubber composition of the present invention becomes a cross-linkable composition, It can be a nitrile rubber composition.
- the crosslinking agent is not particularly limited, and includes, for example, a sulfur-based crosslinking agent and an organic peroxide crosslinking agent.
- a sulfur-based crosslinking agent is preferred.
- Sulfur-based crosslinking agents include sulfur such as powdered sulfur, sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur and insoluble sulfur; sulfur chloride, sulfur dichloride, 4,4′-dithiodimorpholine, and 4,4 ′ -Sulfur-containing compounds such as tetrathiodimorpholine, 4-morpholinyl morpholinodithiothioate, alkylphenol disulfide, dibenzothiazyl disulfide, caprolactam disulfide, phosphorus-containing polysulfide, and high molecular polysulfide; tetramethylthiuram disulfide, selenium dimethyldithiocarbamate Sulfur donating compounds; and the like.
- 4,4′-dithiodimorpholine, 4,4′-tetrathiodimorpholine from the viewpoint that the obtained crosslinkable rubber composition can be more excellent in crosslink stability.
- Sulfur-containing compounds having a morpholine structure such as 4-morpholinyl morpholinodithioformate are preferred, and 4,4'-dithiodimorpholine is particularly preferred.
- the content of the crosslinking agent in the nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the nitrile group-containing copolymer rubber (A). , More preferably 0.2 to 8 parts by weight, even more preferably 0.5 to 6 parts by weight.
- cross-linking assistants such as stearic acid; guanidine-based, thiuram-based, aldehyde- It is preferable to use an amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, or thiourea-based crosslinking accelerator;
- the amount of these crosslinking aids and crosslinking accelerators used is preferably in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the nitrile copolymer rubber (A).
- the nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention may contain other additives such as a crosslinking retarder, an antioxidant, a reinforcing agent, a lubricant, an adhesive, a lubricant, and a processing aid. And additives such as a flame retardant, a fungicide, an antistatic agent, and a coloring agent.
- the nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention contains a rubber other than the nitrile group-containing copolymer rubber (A) as a compounding agent as long as the effects of the present invention are not impaired. May be.
- Examples of the rubber other than the nitrile group-containing copolymer rubber (A) include acrylic rubber, ethylene-acrylic acid copolymer rubber, fluororubber, styrene-butadiene copolymer rubber, polybutadiene rubber, ethylene-propylene copolymer rubber, Examples include ethylene-propylene-diene terpolymer rubber, epichlorohydrin rubber, urethane rubber, chloroprene rubber, silicone rubber, fluorosilicone rubber, chlorosulfonated polyethylene rubber, natural rubber, and polyisoprene rubber.
- the compounding amount is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the nitrile group-containing copolymer rubber (A). And more preferably 10 parts by weight or less.
- the compound Mooney viscosity (ML1 + 4, 100 ° C.) of the nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention is preferably 20 to 150, more preferably 30 to 120, and further preferably 40 to 100.
- a plasticizer (C) having a molecular weight of 500 to 2,000 is compounded, as described above, the ⁇ , ⁇ -ethylenically unsaturated nitrile monopolymer is used as a nitrile group-containing copolymer rubber.
- the nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention is obtained by mixing the above-described nitrile group-containing copolymer rubber (A), vinyl chloride resin (B), and plasticizer (C). Can be manufactured.
- the nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention contains a compounding agent such as a filler or a crosslinking agent
- the following steps are preferably employed. That is, a part of the total amount of the plasticizer (C) contained in the nitrile rubber composition (crosslinkable nitrile rubber composition) is partially converted into a nitrile group-containing copolymer rubber (A) and a vinyl chloride resin (B).
- a first mixing step of mixing In the composition obtained in the first mixing step, the rest of the total amount of the plasticizer (C) contained in the nitrile rubber composition (crosslinkable nitrile rubber composition) and a compounding agent are blended and mixed. It is preferable to include two mixing steps.
- nitrile rubber composition crosslinkable nitrile rubber composition
- nitrile group-containing copolymer rubber (A) and the vinyl chloride resin (B) a compounding agent such as a filler or a cross-linking agent is added together with the remaining plasticizer (C), and the process of mixing is employed to appropriately suppress bleeding of the plasticizer (C). , In a desired amount.
- the plasticizer (C) is used in an amount of preferably 1 to 60 parts by weight, more preferably 3 to 55 parts by weight, and still more preferably 5 to 55 parts by weight, based on 100 parts by weight of the nitrile group-containing copolymer rubber (A).
- the amount can be 50 parts by weight, more preferably 8 to 40 parts by weight, particularly preferably 10 to 40 parts by weight, and most preferably 15 to 30 parts by weight.
- the blending amount of the plasticizer (C) in the first mixing step is 10 to 90% by weight of the total amount of the plasticizer (C) contained in the nitrile rubber composition (crosslinkable nitrile rubber composition). %, Preferably 20 to 90% by weight, more preferably 25 to 85% by weight, and particularly preferably 55 to 75% by weight.
- most of the composition obtained in the first mixing step contains a nitrile group-containing copolymer rubber (A), a vinyl chloride resin (B), and a plasticizer (C). It is preferable that the components are mixed so that the ratio of these components, specifically, the total content of these components is preferably 95% by weight or more, more preferably 99% by weight or more. That is, when the content is preferably 5% by weight or less, more preferably 1% by weight or less, a mode may be adopted in which a compounding agent such as a stabilizer is contained.
- the mixing method in the first mixing step is not particularly limited, but the nitrile group-containing copolymer rubber (A), vinyl chloride resin (B), and plasticizer (C) can be mixed with a Banbury mixer, an intermixer, a kneader, a roll, or the like. And a method of kneading using the same.
- the mixing temperature in the first mixing step is not particularly limited, but is preferably from 40 to 200 ° C, more preferably from 50 to 190 ° C.
- the mixing time in the first mixing step is not particularly limited, but is preferably 3 to 20 minutes, more preferably 5 to 15 minutes.
- the mixing method in the second mixing step is not particularly limited, but the composition obtained in the first mixing step, the plasticizer (C), and the compounding agent such as a filler and a crosslinking agent are mixed with a Banbury mixer, an intermixer, and the like. , A kneader, a roll, or the like.
- a component excluding a crosslinking agent and a component unstable to heat is replaced with a Banbury mixer, an intermixer, a kneader, or the like.
- the method of the present invention is preferably a method in which the mixture is primarily mixed by a mixer, and then transferred to a roll or the like, and a crosslinking agent or a component unstable to heat is added to the mixture to perform a secondary mixing.
- the mixing temperature in the second mixing step (the mixing temperature in the primary mixing and the secondary mixing) is not particularly limited, but is preferably 40 to 100 ° C, more preferably 40 to 80 ° C.
- the mixing time (the total mixing time of the primary mixing and the secondary mixing) in the second mixing step is not particularly limited, but is preferably 3 to 20 minutes, more preferably 3 to 15 minutes.
- the cross-linked rubber of the present invention is obtained by cross-linking the cross-linkable nitrile rubber composition of the present invention described above (that is, a composition obtained by blending a cross-linking agent with the nitrile rubber composition of the present invention).
- the cross-linked rubber of the present invention is formed using the cross-linkable nitrile rubber composition of the present invention, and molded by a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll, and the like, and heated.
- a cross-linking reaction is carried out, and the shape can be fixed as a cross-linked product.
- crosslinking may be performed after molding in advance, or crosslinking may be performed simultaneously with molding.
- the molding temperature is usually from 10 to 200 ° C, preferably from 25 to 120 ° C.
- the crosslinking temperature is usually from 100 to 200 ° C., preferably from 130 to 190 ° C.
- the crosslinking time is usually from 1 minute to 24 hours, preferably from 2 minutes to 1 hour.
- the surface may be crosslinked, but the inside may not be sufficiently crosslinked. Therefore, secondary crosslinking may be performed by further heating.
- a heating method a general method used for rubber crosslinking, such as press heating, steam heating, oven heating, and hot air heating, may be appropriately selected.
- the rubber cross-linked product of the present invention thus obtained is obtained by using the cross-linkable nitrile rubber composition of the present invention described above, wherein the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit described above is used.
- the properties derived from the nitrile group-containing copolymer rubber (A) having a relatively high iodine value and the vinyl chloride resin (B), that is, the obtained rubber cross-linked product has a fuel oil swelling resistance and a fuel resistance. In addition to the properties of being excellent in oil permeability, ozone resistance and heat resistance, it has excellent compression set resistance, compressive stress retention and cold resistance.
- the rubber crosslinked product of the present invention makes use of such characteristics and utilizes O-rings, packings, diaphragms, oil seals, shaft seals, bearing seals, well head seals, shock absorber seals, seals for pneumatic equipment, air conditioners, and the like.
- Seals for rolling devices rolling bearings, automotive hub units, automotive water pumps, linear guide devices, ball screws, etc.), valves and valve seats, various sealing materials such as BOP (Blow Out Preventer) and platters; Intake manifold and sieve Intake manifold gasket to be installed at the connection between cylinder head and cylinder head, cylinder head gasket to be installed at the connection between cylinder block and cylinder head, rocker cover gasket to be installed at the connection between rocker cover and cylinder head, oil pan Oil pan gasket to be attached to cylinder block or connection to transmission case, gasket for fuel cell separator to be fitted between a pair of housings sandwiching unit cell with positive electrode, electrolyte plate and negative electrode, for top cover of hard disk drive Various gaskets such as gaskets; various rolls such as printing rolls
- the crosslinked rubber product of the present invention comprises a nitrile group-containing copolymer rubber (A) having a relatively high ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit and a relatively low iodine value, and vinyl chloride.
- A nitrile group-containing copolymer rubber
- B vinyl chloride
- the resulting rubber cross-linked product is excellent in fuel oil swelling resistance, fuel oil permeation resistance, ozone resistance and heat resistance, as well as compression set resistance. Since it is excellent in compressive stress retention and cold resistance, it can be suitably used for fuel hose applications.
- a laminate of two or more layers having at least one layer made of the crosslinked rubber of the present invention.
- the other layers forming the laminate include fluorine rubber, chloroprene rubber, hydrin rubber, chlorosulfonated polyethylene rubber, acrylic rubber, ethylene-acrylic acid copolymer, ethylene-propylene copolymer, ethylene -Propylene-diene terpolymer, butyl rubber, isoprene rubber, natural rubber, styrene-butadiene copolymer, fluororesin, polyamide resin, polyvinyl alcohol, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin , Polybutylene naphthalate, polyphenylene sulfide, polyolefin resin, polyester resin and the like.
- Mooney viscosity (compound Mooney) of the crosslinkable nitrile rubber composition was measured according to JIS K6300-1 (unit: [ML1 + 4, 100 ° C.]).
- T 10 is the "maximum torque MH- minimum torque ML" is taken as 100%, the torque from the minimum torque ML, means the time required for 10% increase, as the value of T 10 is large, It can be judged that the crosslinking speed is slow and the crosslinking stability is excellent.
- the crosslinkable nitrile rubber composition was placed in a mold having a length of 15 cm, a width of 15 cm, and a depth of 0.2 cm, and press-molded at 160 ° C. for 20 minutes while applying a pressure of 10 MPa to obtain a sheet-like rubber cross-linked product. .
- a test piece was prepared by punching out the obtained sheet cross-linked rubber with a JIS No. 3 dumbbell. Then, using the obtained test piece, the tensile strength and elongation at break of the rubber crosslinked product were measured according to JIS K6251, and a durometer hardness tester (type A) was used according to JIS K6253-3: 2012. The hardness of the rubber crosslinked product was measured in each case.
- ⁇ Compression stress relaxation test> The crosslinkable nitrile rubber composition was pressed using a mold at a temperature of 160 ° C. for 30 minutes while applying pressure, thereby obtaining a columnar rubber crosslinked product having a diameter of 29 mm and a height of 12.5 mm. Then, a compression stress relaxation test was performed by maintaining the obtained crosslinked rubber in an environment of 125 ° C. in a state of being compressed by 25%. Then, 30 minutes after the start of the test, the compressive stress of the rubber crosslinked product was measured, and this was taken as the initial stress. The compressive stress 72 hours after the start of the test was measured, and the compressive stress retention was determined according to the following equation. .
- Compressive stress retention [%] (Compressive stress [MPa] after 72 hours / Initial stress [MPa]) ⁇ 100
- ⁇ Compressive stress retention
- Example 1 (First mixing step) Using a Banbury mixer, 30 parts of hydrogenated acrylonitrile-butadiene rubber (A-1) (trade name “Zetpol 0020”, acrylonitrile monomer unit 49% by weight, iodine value 23), hydrogenated acrylonitrile-butadiene rubber (A- 2) 30 parts of (trade name “Zetpol 1020”, acrylonitrile monomer unit 44% by weight, iodine value 24) 30 parts, vinyl chloride resin (trade name "TK1300", Shin-Etsu Chemical Co., Ltd., average polymerization degree 1300) 40 parts, 0.5 parts of a calcium-magnesium-zinc-based stabilizer (trade name “ADEKA STAB RUP-110”, manufactured by ADEKA) and polyetherester (c1-1) (trade name “ADEKA SIZER RS-700”, manufactured by ADEKA) Molecular weight: 550, viscosity at 25 ° C .: 30 mPa
- the mixture of the hydrogenated acrylonitrile-butadiene rubber (A-1) and the hydrogenated acrylonitrile-butadiene rubber (A-2) has an acrylonitrile monomer unit amount of 46.5% by weight and an iodine value of the mixture. 23.5.
- Example 2 In the first mixing step and the second mixing step, the plasticizer was replaced with polyetherester (c1-1) (trade name “ADEKASIZER RS-700”, manufactured by ADEKA), and both were mixed with polyetherester (c1). -2) (trade name “ADEKA SIZER RS-735", manufactured by ADEKA Corporation, molecular weight: 850, viscosity at 25 ° C: 80 mPa ⁇ s, flash point: 252 ° C, polyether ester represented by the above general formula (1))
- c1-1 polyetherester
- -2 trade name “ADEKA SIZER RS-735”
- a crosslinkable nitrile rubber composition was obtained and evaluated in the same manner as in Example 1 except that the same amount of (c1)) was used. Table 1 shows the results.
- Example 3 In the first mixing step and the second mixing step, as the plasticizer, in place of the polyetherester (c1-1) (trade name “ADEKASIZER RS-700”, manufactured by ADEKA Corporation), any of adipic acid-based polyester ( c2-1) (trade name “ADEKASIZER PN-170”, manufactured by ADEKA Corporation, molecular weight: 1100, viscosity at 25 ° C .: 800 mPa ⁇ s, flash point: 244 ° C., adipic acid-based polyester (c2)) used in the same amount
- a crosslinkable nitrile rubber composition was obtained in the same manner as in Example 1 except that the evaluation was performed, and the evaluation was performed in the same manner. Table 1 shows the results.
- Example 4 In the second mixing step, the same procedure as in Example 1 was carried out, except that 15 parts of a calcium-magnesium-zinc-based stabilizer (trade name “ADK STAB RUP-110”, manufactured by ADEKA) was used instead of 5 parts of zinc oxide. Thus, a crosslinkable nitrile rubber composition was obtained and similarly evaluated. Table 1 shows the results.
- adipic acid polyether ester was used instead of polyether ester (c1-1) (trade name “ADEKASIZER RS-700” manufactured by ADEKA). (Product name “ADEKASIZER RS-107”, manufactured by ADEKA Corporation, molecular weight: 434, viscosity at 25 ° C .: 20 mPa ⁇ s, flash point: 215 ° C.), except that the same amount was used. A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner. Table 1 shows the results.
- nitrile group-containing copolymer rubber (A) containing ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units at a ratio of 40 to 50% by weight and an iodine value of 5 to 50
- the nitrile rubber composition crosslinkable nitrile rubber composition
- the vinyl chloride resin (B) and the plasticizer (C) having a molecular weight of 500 to 2,000
- the compound Mooney viscosity increases.
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Abstract
Provided is a nitrile rubber composition which comprises a nitrile-group-containing copolymer rubber (A) containing units of an α,β-ethylenically unsaturated nitrile monomer in an amount of 40-50 wt% and having an iodine value of 5-50, a vinyl chloride resin (B), and a plasticizer (C) having a molecular weight of 500-2,000.
Description
本発明は、加工性に優れ、かつ、耐圧縮永久歪み性、圧縮応力保持率および耐寒性に優れたゴム架橋物を与えることのできるニトリルゴム組成物、ならびに、このようなニトリルゴム組成物を用いて得られる架橋性ニトリルゴム組成物およびゴム架橋物に関する。また、本発明は、このようなニトリルゴム組成物を製造するための方法にも関する。
The present invention provides a nitrile rubber composition which is excellent in processability, and can provide a rubber crosslinked product having excellent compression set resistance, compression stress retention and cold resistance, and a nitrile rubber composition such as this. The present invention relates to a crosslinkable nitrile rubber composition and a crosslinked rubber obtained by using the composition. The invention also relates to a method for producing such a nitrile rubber composition.
従来から、α,β-エチレン性不飽和ニトリル単量体単位、および共役ジエン単量体単位を含有するゴム(ニトリル基含有共重合体ゴム)は、耐燃料油性に優れるゴムとして知られており、主に燃料ホース、ガスケット、パッキン、オイルシールなど自動車の各種油類まわりのゴム製品の材料として用いられている。
Conventionally, rubbers containing an α, β-ethylenically unsaturated nitrile monomer unit and a conjugated diene monomer unit (copolymer rubber containing a nitrile group) are known as rubbers having excellent fuel oil resistance. It is mainly used as a material for rubber products around various oils of automobiles such as fuel hoses, gaskets, packings, oil seals and the like.
たとえば、ニトリル基含有共重合体ゴムに、塩化ビニル樹脂を配合することで、耐燃料油性に優れることに加えて、耐オゾン性などを向上させることができることから、燃料ホース用途に好適に用いられている(たとえば、特許文献1参照)。
For example, by blending a vinyl chloride resin with a nitrile group-containing copolymer rubber, in addition to having excellent fuel oil resistance, it is possible to improve ozone resistance and the like, so that it is suitably used for fuel hose applications. (For example, see Patent Document 1).
一方で、燃料ホースなど自動車の各種油類まわりのゴム製品においては、さらなる耐燃料油性や耐熱性が求められており、耐燃料油性および耐熱性のさらなる向上という観点からは、ニトリル基含有共重合体ゴム中におけるニトリル基含有単量体量を増加させるとともに、ニトリル基含有共重合体ゴムを水素化することが有効である。しかしながら、ニトリル基含有共重合体ゴム中におけるニトリル基含有単量体量を増加させたり、水素化した場合には、塩化ビニル樹脂とブレンドした際に硬くなり、加工性が低下してしまうという課題があった。
On the other hand, rubber products such as fuel hoses and other types of automobile oils are required to have further resistance to fuel oil and heat resistance. From the viewpoint of further improving fuel oil resistance and heat resistance, a nitrile group-containing copolymer is required. It is effective to increase the amount of the nitrile group-containing monomer in the combined rubber and to hydrogenate the nitrile group-containing copolymer rubber. However, when the amount of the nitrile group-containing monomer in the nitrile group-containing copolymer rubber is increased or when hydrogenated, it becomes hard when blended with a vinyl chloride resin, resulting in reduced workability. was there.
これに対し、本発明者等が検討したところ、耐燃料油性および耐熱性のさらなる向上を実現するために、ニトリル基含有共重合体ゴムとして、α,β-エチレン性不飽和ニトリル単量体単位を40~50重量%と比較的高い割合で含有し、かつ、ヨウ素価が5~50の範囲にあるものを用いた場合でも、塩化ビニル樹脂に加えて、分子量が500~2000である可塑剤を組み合わせることで、硬くなることにより加工性が低下してしまうことを有効に防止できること、さらには、このようなゴム組成物を用いて得られるゴム架橋物が、耐圧縮永久歪み性、圧縮応力保持率および耐寒性に優れたものであることを見出し、本発明を完成させるに至った。
On the other hand, the present inventors have studied and found that α, β-ethylenically unsaturated nitrile monomer units were used as a nitrile group-containing copolymer rubber in order to further improve fuel oil resistance and heat resistance. , A plasticizer having a molecular weight of 500 to 2,000 in addition to the vinyl chloride resin, even when a resin having a relatively high ratio of 40 to 50% by weight and an iodine value in the range of 5 to 50 is used. By combining, it can be effectively prevented that the workability is reduced by becoming harder, and further, a rubber crosslinked product obtained by using such a rubber composition has a compression set resistance, a compression stress The inventors have found that they have excellent retention and cold resistance, and have completed the present invention.
すなわち、本発明によれば、α,β-エチレン性不飽和ニトリル単量体単位を40~50重量%の割合で含有し、ヨウ素価が5~50であるニトリル基含有共重合体ゴム(A)と、塩化ビニル樹脂(B)と、分子量が500~2000である可塑剤(C)と、を含有するニトリルゴム組成物が提供される。
That is, according to the present invention, a nitrile group-containing copolymer rubber (A) containing α, β-ethylenically unsaturated nitrile monomer units at a ratio of 40 to 50% by weight and an iodine value of 5 to 50 is used. ), A vinyl chloride resin (B), and a plasticizer (C) having a molecular weight of 500 to 2,000.
本発明のニトリルゴム組成物において、前記可塑剤(C)が、下記一般式(1)で表されるポリエーテルエステル(c1)であることが好ましい。
(上記一般式(1)中、R1は、それぞれ独立して、水素原子、または炭素数1~20の炭化水素基、R2は、それぞれ独立して、水素原子、または炭素数1~6の炭化水素基であり、nは1~40の整数である。)
本発明のニトリルゴム組成物において、前記可塑剤(C)が、分子量が800~2000であり、温度25℃における粘度が50~1500mPa・sであるアジピン酸系ポリエステル(c2)であることが好ましい。
本発明のニトリルゴム組成物において、前記ニトリル基含有共重合体ゴム(A)100重量部に対する、前記可塑剤(C)の含有量が1~60重量部であることが好ましい。 In the nitrile rubber composition of the present invention, the plasticizer (C) is preferably a polyetherester (c1) represented by the following general formula (1).
(In the above general formula (1), R 1 is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 is each independently a hydrogen atom or a 1 to 6 carbon atom. And n is an integer of 1 to 40.)
In the nitrile rubber composition of the present invention, the plasticizer (C) is preferably an adipic acid-based polyester (c2) having a molecular weight of 800 to 2,000 and a viscosity at 25 ° C. of 50 to 1500 mPa · s. .
In the nitrile rubber composition of the present invention, the content of the plasticizer (C) is preferably 1 to 60 parts by weight based on 100 parts by weight of the nitrile group-containing copolymer rubber (A).
本発明のニトリルゴム組成物において、前記可塑剤(C)が、分子量が800~2000であり、温度25℃における粘度が50~1500mPa・sであるアジピン酸系ポリエステル(c2)であることが好ましい。
本発明のニトリルゴム組成物において、前記ニトリル基含有共重合体ゴム(A)100重量部に対する、前記可塑剤(C)の含有量が1~60重量部であることが好ましい。 In the nitrile rubber composition of the present invention, the plasticizer (C) is preferably a polyetherester (c1) represented by the following general formula (1).
In the nitrile rubber composition of the present invention, the plasticizer (C) is preferably an adipic acid-based polyester (c2) having a molecular weight of 800 to 2,000 and a viscosity at 25 ° C. of 50 to 1500 mPa · s. .
In the nitrile rubber composition of the present invention, the content of the plasticizer (C) is preferably 1 to 60 parts by weight based on 100 parts by weight of the nitrile group-containing copolymer rubber (A).
本発明によれば、上記本発明のニトリルゴム組成物と、架橋剤とを含有する架橋性ニトリルゴム組成物が提供される。
さらに、本発明によれば、上記本発明の架橋性ニトリルゴム組成物を架橋してなるゴム架橋物が提供される。 According to the present invention, there is provided a crosslinkable nitrile rubber composition comprising the above nitrile rubber composition of the present invention and a crosslinking agent.
Further, according to the present invention, there is provided a cross-linked rubber obtained by cross-linking the cross-linkable nitrile rubber composition of the present invention.
さらに、本発明によれば、上記本発明の架橋性ニトリルゴム組成物を架橋してなるゴム架橋物が提供される。 According to the present invention, there is provided a crosslinkable nitrile rubber composition comprising the above nitrile rubber composition of the present invention and a crosslinking agent.
Further, according to the present invention, there is provided a cross-linked rubber obtained by cross-linking the cross-linkable nitrile rubber composition of the present invention.
また、本発明によれば、α,β-エチレン性不飽和ニトリル単量体単位を40~50重量%の割合で含有し、ヨウ素価が5~50であるニトリル基含有共重合体ゴム(A)と、塩化ビニル樹脂(B)と、分子量が500~2000である可塑剤(C)と、配合剤とを含有するニトリルゴム組成物を製造する方法であって、
前記ニトリルゴム組成物中に含有させる前記可塑剤(C)の全量のうち一部を、前記ニトリル基含有共重合体ゴム(A)と、前記塩化ビニル樹脂(B)と混合する第1の混合工程と、
前記第1の混合工程において得られた組成物に、前記ニトリルゴム組成物に含有させる前記可塑剤(C)の全量のうち残部と、前記配合剤とを配合し、混合する第2混合工程とを備えるニトリルゴム組成物の製造方法が提供される。 Further, according to the present invention, a nitrile group-containing copolymer rubber (A) containing an α, β-ethylenically unsaturated nitrile monomer unit at a ratio of 40 to 50% by weight and an iodine value of 5 to 50 is used. ), A vinyl chloride resin (B), a plasticizer (C) having a molecular weight of 500 to 2,000, and a compounding agent, the method comprising producing a nitrile rubber composition,
First mixing in which a part of the total amount of the plasticizer (C) to be contained in the nitrile rubber composition is mixed with the nitrile group-containing copolymer rubber (A) and the vinyl chloride resin (B). Process and
A second mixing step in which the composition obtained in the first mixing step is mixed with the rest of the total amount of the plasticizer (C) to be contained in the nitrile rubber composition and the compounding agent, and a second mixing step is performed. A method for producing a nitrile rubber composition comprising:
前記ニトリルゴム組成物中に含有させる前記可塑剤(C)の全量のうち一部を、前記ニトリル基含有共重合体ゴム(A)と、前記塩化ビニル樹脂(B)と混合する第1の混合工程と、
前記第1の混合工程において得られた組成物に、前記ニトリルゴム組成物に含有させる前記可塑剤(C)の全量のうち残部と、前記配合剤とを配合し、混合する第2混合工程とを備えるニトリルゴム組成物の製造方法が提供される。 Further, according to the present invention, a nitrile group-containing copolymer rubber (A) containing an α, β-ethylenically unsaturated nitrile monomer unit at a ratio of 40 to 50% by weight and an iodine value of 5 to 50 is used. ), A vinyl chloride resin (B), a plasticizer (C) having a molecular weight of 500 to 2,000, and a compounding agent, the method comprising producing a nitrile rubber composition,
First mixing in which a part of the total amount of the plasticizer (C) to be contained in the nitrile rubber composition is mixed with the nitrile group-containing copolymer rubber (A) and the vinyl chloride resin (B). Process and
A second mixing step in which the composition obtained in the first mixing step is mixed with the rest of the total amount of the plasticizer (C) to be contained in the nitrile rubber composition and the compounding agent, and a second mixing step is performed. A method for producing a nitrile rubber composition comprising:
本発明のニトリルゴム組成物の製造方法において、前記第1混合工程における前記可塑剤(C)の配合量を、前記ニトリルゴム組成物中に含有させる前記可塑剤(C)の全量のうち、10~90重量%とすることが好ましい。
本発明のニトリルゴム組成物の製造方法において、前記配合剤が、少なくとも充填剤を含むものであることが好ましい。 In the method for producing a nitrile rubber composition of the present invention, the blending amount of the plasticizer (C) in the first mixing step is 10% of the total amount of the plasticizer (C) contained in the nitrile rubber composition. It is preferable to set it to 90% by weight.
In the method for producing a nitrile rubber composition of the present invention, the compounding agent preferably contains at least a filler.
本発明のニトリルゴム組成物の製造方法において、前記配合剤が、少なくとも充填剤を含むものであることが好ましい。 In the method for producing a nitrile rubber composition of the present invention, the blending amount of the plasticizer (C) in the first mixing step is 10% of the total amount of the plasticizer (C) contained in the nitrile rubber composition. It is preferable to set it to 90% by weight.
In the method for producing a nitrile rubber composition of the present invention, the compounding agent preferably contains at least a filler.
本発明によれば、加工性に優れ、かつ、耐圧縮永久歪み性、圧縮応力保持率および耐寒性に優れたゴム架橋物を与えることのできるニトリルゴム組成物を提供することができる。また、本発明によれば、このようなニトリルゴム組成物を用いて得られる架橋性ニトリルゴム組成物およびゴム架橋物、ならびに、このようなニトリルゴム組成物を製造するための方法を提供することもできる。
According to the present invention, it is possible to provide a nitrile rubber composition which is excellent in processability and can give a rubber crosslinked product having excellent compression set resistance, compression stress retention and cold resistance. Further, according to the present invention, there is provided a crosslinkable nitrile rubber composition and a rubber crosslinked product obtained by using such a nitrile rubber composition, and a method for producing such a nitrile rubber composition. Can also.
本発明のニトリルゴム組成物は、α,β-エチレン性不飽和ニトリル単量体単位を40~50重量%の割合で含有し、ヨウ素価が5~50であるニトリル基含有共重合体ゴム(A)と、塩化ビニル樹脂(B)と、分子量が500~2000である可塑剤(C)と、を含有する。
The nitrile rubber composition of the present invention contains a nitrile group-containing copolymer rubber containing an α, β-ethylenically unsaturated nitrile monomer unit at a ratio of 40 to 50% by weight and an iodine value of 5 to 50 ( A), a vinyl chloride resin (B), and a plasticizer (C) having a molecular weight of 500 to 2,000.
<ニトリル基含有共重合体ゴム(A)>
本発明で用いるニトリル基含有共重合体ゴム(A)は、α,β-エチレン性不飽和ニトリル単量体単位を40~50重量%の割合で含有し、ヨウ素価が5~50の範囲にあるものである。 <Nitrile group-containing copolymer rubber (A)>
The nitrile group-containing copolymer rubber (A) used in the present invention contains an α, β-ethylenically unsaturated nitrile monomer unit in a proportion of 40 to 50% by weight, and has an iodine value in a range of 5 to 50. There is something.
本発明で用いるニトリル基含有共重合体ゴム(A)は、α,β-エチレン性不飽和ニトリル単量体単位を40~50重量%の割合で含有し、ヨウ素価が5~50の範囲にあるものである。 <Nitrile group-containing copolymer rubber (A)>
The nitrile group-containing copolymer rubber (A) used in the present invention contains an α, β-ethylenically unsaturated nitrile monomer unit in a proportion of 40 to 50% by weight, and has an iodine value in a range of 5 to 50. There is something.
本発明で用いるニトリル基含有共重合体ゴム(A)中に含有される、α,β-エチレン性不飽和ニトリル単量体単位を形成するα,β-エチレン性不飽和ニトリル単量体は、特に限定されず、アクリロニトリル;α-クロロアクリロニトリル、α-ブロモアクリロニトリルなどのα-ハロゲノアクリロニトリル;メタクリロニトリル、エタクリロニトリルなどのα-アルキルアクリロニトリル;などが挙げられる。これらのなかでも、アクリロニトリルおよびメタクリロニトリルが好ましく、アクリロニトリルが特に好ましい。α,β-エチレン性不飽和ニトリル単量体は一種を単独で用いてもよく、二種以上を併用してもよい。
The α, β-ethylenically unsaturated nitrile monomer which forms the α, β-ethylenically unsaturated nitrile monomer unit contained in the nitrile group-containing copolymer rubber (A) used in the present invention is: There is no particular limitation, and acrylonitrile; α-halogenoacrylonitrile such as α-chloroacrylonitrile and α-bromoacrylonitrile; α-alkylacrylonitrile such as methacrylonitrile and ethacrylonitrile; Among these, acrylonitrile and methacrylonitrile are preferred, and acrylonitrile is particularly preferred. The α, β-ethylenically unsaturated nitrile monomer may be used alone or in combination of two or more.
本発明で用いるニトリル基含有共重合体ゴム(A)中における、α,β-エチレン性不飽和ニトリル単量体単位の含有量は、全単量体単位に対して、40~50重量%であり、好ましくは42~50重量%、より好ましくは44~50重量%、さらに好ましくは44~49重量%、さらにより好ましくは44~48重量%である。α,β-エチレン性不飽和ニトリル単量体単位の含有量を上記範囲とすることにより、得られるゴム架橋物を耐燃料油性に優れるものとすることができる。α,β-エチレン性不飽和ニトリル単量体単位の含有量が少なすぎると、得られるゴム架橋物が耐燃料油性に劣るものとなるおそれがあり、逆に多すぎると耐寒性が低下する可能性がある。なお、ニトリル基含有共重合体ゴム(A)として、単量体組成の異なるゴムを組み合わせて用いる場合には、単量体組成の異なるゴムの混合物全体における、α,β-エチレン性不飽和ニトリル単量体単位の含有割合を上記範囲とすればよい(後述する、ジエン単量体単位および/またはα-オレフィン単量体単位を含む、共重合可能な単量体の単位においても同様。)。
The content of α, β-ethylenically unsaturated nitrile monomer units in the nitrile group-containing copolymer rubber (A) used in the present invention is 40 to 50% by weight based on all monomer units. And preferably 42 to 50% by weight, more preferably 44 to 50% by weight, still more preferably 44 to 49% by weight, and still more preferably 44 to 48% by weight. By setting the content of the α, β-ethylenically unsaturated nitrile monomer unit in the above range, the obtained cross-linked rubber can have excellent fuel oil resistance. If the content of the α, β-ethylenically unsaturated nitrile monomer unit is too small, the obtained rubber cross-linked product may be inferior in fuel oil resistance, while if too large, the cold resistance may be reduced. There is. When rubbers having different monomer compositions are used in combination as the nitrile group-containing copolymer rubber (A), α, β-ethylenically unsaturated nitrile in the entire mixture of rubbers having different monomer compositions is used. The content ratio of the monomer unit may be within the above range (the same applies to a copolymerizable monomer unit including a diene monomer unit and / or an α-olefin monomer unit described later). .
また、本発明のニトリル基含有共重合体ゴムは、ゴム弾性による機械的特性の向上の観点から、ジエン単量体単位および/またはα-オレフィン単量体単位をさらに含有していることが好ましい。
In addition, the nitrile group-containing copolymer rubber of the present invention preferably further contains a diene monomer unit and / or an α-olefin monomer unit from the viewpoint of improving mechanical properties due to rubber elasticity. .
ジエン単量体単位を形成するジエン単量体としては、1,3-ブタジエン、イソプレン、2,3-ジメチル-1,3-ブタジエン、1,3-ペンタジエン等の炭素数が4以上の共役ジエン;1,4-ペンタジエン、1,4-ヘキサジエン等の炭素数が5~12の非共役ジエンが挙げられる。これらの中では共役ジエンが好ましく、1,3-ブタジエンがより好ましい。α-オレフィン単量体単位を形成するα-オレフィン単量体としては、好ましくは炭素数が2~12のものであり、エチレン、プロピレン、1-ブテン、4-メチル-1-ペンテン、1-ヘキセン、1-オクテン等が例示される。これらのジエン単量体、α-オレフィン単量体は一種を単独で用いてもよく、二種以上を併用してもよい。
Examples of the diene monomer forming the diene monomer unit include conjugated dienes having 4 or more carbon atoms, such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Non-conjugated dienes having 5 to 12 carbon atoms, such as 1,4-pentadiene and 1,4-hexadiene; Of these, conjugated dienes are preferred, and 1,3-butadiene is more preferred. The α-olefin monomer forming the α-olefin monomer unit preferably has 2 to 12 carbon atoms and includes ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1- Hexene, 1-octene and the like are exemplified. One of these diene monomers and α-olefin monomers may be used alone, or two or more thereof may be used in combination.
本発明で用いるニトリル基含有共重合体ゴム(A)中における、ジエン単量体単位および/またはα-オレフィン単量体単位の含有量は、全単量体単位に対して、その下限が、好ましくは40重量%以上、より好ましくは50重量%以上、さらに好ましくは51重量%以上、さらにより好ましくは52重量%以上であり、その上限が、好ましくは60重量%以下、より好ましくは58重量%以下、さらに好ましくは56重量%以下である。ジエン単量体単位および/またはα-オレフィン単量体単位の含有量を上記範囲とすることにより、得られるゴム架橋物を、耐熱性や耐化学的安定性を良好に保ちながら、ゴム弾性に優れたものとすることができる。
In the nitrile group-containing copolymer rubber (A) used in the present invention, the lower limit of the content of the diene monomer unit and / or the α-olefin monomer unit is based on all monomer units. It is preferably at least 40% by weight, more preferably at least 50% by weight, still more preferably at least 51% by weight, still more preferably at least 52% by weight, and the upper limit thereof is preferably at most 60% by weight, more preferably at least 58% by weight. %, More preferably 56% by weight or less. By setting the content of the diene monomer unit and / or the α-olefin monomer unit within the above range, the obtained rubber cross-linked product can have rubber elasticity while maintaining good heat resistance and chemical stability. It can be excellent.
また、本発明で用いるニトリル基含有共重合体ゴム(A)は、上記α,β-エチレン性不飽和ニトリル単量体単位、およびジエン単量体単位またはα-オレフィン単量体単位以外に、これらの単量体単位を形成する単量体と共重合可能な他の単量体の単位を含有していてもよい。このような他の単量体単位の含有割合は、全単量体単位に対して、好ましくは30重量%以下、より好ましくは20重量%以下、さらに好ましくは10重量%以下である。
Further, the nitrile group-containing copolymer rubber (A) used in the present invention may contain, in addition to the above α, β-ethylenically unsaturated nitrile monomer unit, a diene monomer unit and an α-olefin monomer unit, It may contain units of other monomers copolymerizable with the monomers forming these monomer units. The content ratio of such another monomer unit is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less, based on all monomer units.
このような共重合可能な他の単量体としては、たとえば、スチレン、α-メチルスチレン、ビニルトルエンなどの芳香族ビニル化合物;フルオロエチルビニルエーテル、フルオロプロピルビニルエーテル、o-トリフルオロメチルスチレン、ペンタフルオロ安息香酸ビニル、ジフルオロエチレン、テトラフルオロエチレンなどのフッ素含有ビニル化合物;エチレン、プロピレン、1-ブテン、4-メチル-1-ペンテン、1-ヘキセン、1-オクテンなどのα-オレフィン化合物;アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、フマル酸、無水フマル酸などのα,β-エチレン性不飽和モノカルボン酸およびその無水物;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸2-エチルヘキシルなどのα,β-エチレン性不飽和モノカルボン酸アルキルエステル;マレイン酸モノエチル、マレイン酸ジエチル、マレイン酸モノブチル、マレイン酸ジブチル、フマル酸モノエチル、フマル酸ジエチル、フマル酸モノブチル、フマル酸ジブチル、フマル酸モノシクロヘキシル、フマル酸ジシクロヘキシル、イタコン酸モノエチル、イタコン酸ジエチル、イタコン酸モノブチル、イタコン酸ジブチルなどのα,β-エチレン性不飽和多価カルボン酸のモノエステルおよびジエステル;(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸メトキシプロピル、(メタ)アクリル酸ブトキシエチルなどのα,β-エチレン性不飽和カルボン酸のアルコキシアルキルエステル;(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸3-ヒドロキシプロピルなどのα,β-エチレン性不飽和カルボン酸のヒドロキシアルキルエステル;ジビニルベンゼンなどのジビニル化合物;エチレンジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレートなどのジ(メタ)アクリル酸エステル類;トリメチロールプロパントリ(メタ)アクリレートなどのトリメタクリル酸エステル類;などの多官能エチレン性不飽和単量体のほか、N-メチロール(メタ)アクリルアミド、N,N’-ジメチロール(メタ)アクリルアミドなどの自己架橋性化合物;などが挙げられる。これらの共重合可能な他の単量体は一種を単独で用いてもよく、二種以上を併用してもよい。
Such other copolymerizable monomers include, for example, aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethylstyrene, pentafluoro Fluorine-containing vinyl compounds such as vinyl benzoate, difluoroethylene and tetrafluoroethylene; α-olefin compounds such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene; acrylic acid; Α, β-ethylenically unsaturated monocarboxylic acids such as methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, fumaric anhydride and anhydrides thereof; methyl (meth) acrylate, (meth) ) Ethyl acrylate, (meth) acrylic acid Acetyl, α, β-ethylenically unsaturated monocarboxylic acid alkyl esters such as 2-ethylhexyl (meth) acrylate; monoethyl maleate, diethyl maleate, monobutyl maleate, dibutyl maleate, monoethyl fumarate, diethyl fumarate, Monoesters of α, β-ethylenically unsaturated polycarboxylic acids such as monobutyl fumarate, dibutyl fumarate, monocyclohexyl fumarate, dicyclohexyl fumarate, monoethyl itaconate, diethyl itaconate, monobutyl itaconate and dibutyl itaconate; Diester; alkoxyalkyl ester of α, β-ethylenically unsaturated carboxylic acid such as methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, butoxyethyl (meth) acrylate; (meth) acrylic acid 2 Hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as hydroxyethyl and 3-hydroxypropyl (meth) acrylate; divinyl compounds such as divinylbenzene; ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, ethylene Polyfunctional ethylenically unsaturated monomers such as di (meth) acrylates such as glycol di (meth) acrylate; trimethacrylates such as trimethylolpropane tri (meth) acrylate; and N-methylol Self-crosslinking compounds such as (meth) acrylamide and N, N′-dimethylol (meth) acrylamide; and the like. One of these other copolymerizable monomers may be used alone, or two or more thereof may be used in combination.
本発明で用いるニトリル基含有共重合体ゴム(A)のヨウ素価は、5~50であり、好ましくは8~45、より好ましくは10~40、さらに好ましくは18~30である。ニトリル基含有共重合体ゴム(A)のヨウ素価が高すぎると、得られるゴム架橋物の耐熱性および耐オゾン性が低下するおそれがあり、ヨウ素価が低すぎると、得られるゴム架橋物の機械特性が低下するおそれがある。特に、架橋剤として、硫黄系架橋剤を用いた場合には、ヨウ素価を上記範囲とすることにより、加硫を良好かつ適切なものとすることができるため、得られるゴム架橋物を、優れた耐熱性を維持しつつ、耐圧縮永久歪み性、および圧縮応力保持率により優れたものとすることができる。なお、ニトリル基含有共重合体ゴム(A)として、ヨウ素価の異なるゴムを組み合わせて用いる場合には、ヨウ素価の異なるゴムの混合物全体における、ヨウ素価を上記範囲とすればよい。
ニ The nitrile group-containing copolymer rubber (A) used in the present invention has an iodine value of 5 to 50, preferably 8 to 45, more preferably 10 to 40, and still more preferably 18 to 30. If the iodine value of the nitrile group-containing copolymer rubber (A) is too high, the heat resistance and ozone resistance of the obtained rubber cross-linked product may be reduced, and if the iodine value is too low, the obtained rubber cross-linked product Mechanical properties may be reduced. In particular, when a sulfur-based cross-linking agent is used as the cross-linking agent, by setting the iodine value within the above range, vulcanization can be made good and appropriate, so that the obtained rubber cross-linked product is excellent. While maintaining excellent heat resistance, it is possible to obtain more excellent compression set resistance and compression stress retention. In the case where rubbers having different iodine values are used in combination as the nitrile group-containing copolymer rubber (A), the iodine value of the entire mixture of rubbers having different iodine values may be within the above range.
本発明で用いるニトリル基含有共重合体ゴム(A)のポリマー・ムーニー粘度(ML1+4、100℃)は、好ましくは10~200、より好ましくは15~150、さらに好ましくは15~100である。ニトリル基含有共重合体ゴム(A)のポリマー・ムーニー粘度を上記範囲とすることにより、ニトリルゴム組成物の加工性を良好に保ちながら、得られるゴム架橋物の機械特性をより高めることができる。
ポ リ マ ー The polymer Mooney viscosity (ML1 + 4, 100 ° C.) of the nitrile group-containing copolymer rubber (A) used in the present invention is preferably 10 to 200, more preferably 15 to 150, and still more preferably 15 to 100. By setting the polymer Mooney viscosity of the nitrile group-containing copolymer rubber (A) within the above range, it is possible to further improve the mechanical properties of the rubber crosslinked product obtained while maintaining good processability of the nitrile rubber composition. .
なお、ニトリル基含有共重合体ゴム(A)としては、一種のゴムを用いてもよいし、あるいは、二種以上のゴムを併用してもよいが、二種以上のゴムを併用する場合には、それらの特性値の平均値(その使用量を加味した、特性値の平均値)が上記した範囲内にあればよいが、使用する二種以上のゴムのぞれぞれの特性値が、上記した範囲にあることが好ましい。
As the nitrile group-containing copolymer rubber (A), one kind of rubber may be used, or two or more kinds of rubbers may be used in combination. It suffices that the average value of these characteristic values (the average value of the characteristic values taking into account the amount used) be within the above range, but the characteristic value of each of the two or more rubbers used is , Preferably within the above range.
本発明で用いるニトリル基含有共重合体ゴム(A)の製造方法は、特に限定されないが、上述した単量体を共重合し、必要に応じて、得られる共重合体中の炭素-炭素二重結合を水素化することによって製造することができる。重合方法は、特に限定されず公知の乳化重合法や溶液重合法によればよいが、工業的生産性の観点から乳化重合法が好ましい。乳化重合に際しては、乳化剤、重合開始剤、分子量調整剤に加えて、通常用いられる重合副資材を使用することができる。
The method for producing the nitrile group-containing copolymer rubber (A) used in the present invention is not particularly limited, but the above-mentioned monomers are copolymerized, and if necessary, the carbon-carbon dimer in the resulting copolymer is obtained. It can be produced by hydrogenating a heavy bond. The polymerization method is not particularly limited, and may be a known emulsion polymerization method or a solution polymerization method. From the viewpoint of industrial productivity, the emulsion polymerization method is preferable. At the time of emulsion polymerization, a commonly used polymerization auxiliary material can be used in addition to the emulsifier, the polymerization initiator, and the molecular weight modifier.
<塩化ビニル樹脂(B)>
本発明で用いる塩化ビニル樹脂(B)は、樹脂を構成する主構成単量体が塩化ビニルであるものであればよいが、塩化ビニル単量体単位の含有量が50~100重量%であるものが好ましく、60~100重量%であるものがより好ましく、70~100重量%であるものがさらに好ましい。塩化ビニル樹脂(B)を配合することで、得られるゴム架橋物を、耐オゾン性、耐燃料油膨潤性、および耐燃料油透過性に優れたものとすることができる。 <Vinyl chloride resin (B)>
The vinyl chloride resin (B) used in the present invention may be any one as long as the main constituent monomer constituting the resin is vinyl chloride, and the content of the vinyl chloride monomer unit is 50 to 100% by weight. Preferably, it is 60 to 100% by weight, more preferably 70 to 100% by weight. By blending the vinyl chloride resin (B), the obtained rubber crosslinked product can be excellent in ozone resistance, fuel oil swelling resistance, and fuel oil permeability.
本発明で用いる塩化ビニル樹脂(B)は、樹脂を構成する主構成単量体が塩化ビニルであるものであればよいが、塩化ビニル単量体単位の含有量が50~100重量%であるものが好ましく、60~100重量%であるものがより好ましく、70~100重量%であるものがさらに好ましい。塩化ビニル樹脂(B)を配合することで、得られるゴム架橋物を、耐オゾン性、耐燃料油膨潤性、および耐燃料油透過性に優れたものとすることができる。 <Vinyl chloride resin (B)>
The vinyl chloride resin (B) used in the present invention may be any one as long as the main constituent monomer constituting the resin is vinyl chloride, and the content of the vinyl chloride monomer unit is 50 to 100% by weight. Preferably, it is 60 to 100% by weight, more preferably 70 to 100% by weight. By blending the vinyl chloride resin (B), the obtained rubber crosslinked product can be excellent in ozone resistance, fuel oil swelling resistance, and fuel oil permeability.
塩化ビニル樹脂(B)の重合度は、特に限定されないが、JIS K6720-2:1999に規定の溶液粘度法によって測定した平均重合度が、好ましくは400~3000、より好ましくは600~2000である。平均重合度が上記範囲にあると、ニトリルゴム組成物の加工性を良好なものとしながら、得られるゴム架橋物の耐オゾン性、耐燃料油膨潤性、および耐燃料油透過性をより高めることができる。
The degree of polymerization of the vinyl chloride resin (B) is not particularly limited, but the average degree of polymerization measured by a solution viscosity method prescribed in JIS K6720-2: 1999 is preferably 400 to 3000, more preferably 600 to 2000. . When the average degree of polymerization is in the above range, the ozone resistance, fuel oil swelling resistance, and fuel oil permeability of the obtained rubber cross-linked product are further improved while improving the processability of the nitrile rubber composition. Can be.
本発明のニトリルゴム組成物中における、塩化ビニル樹脂(B)の含有量は、ニトリル基含有共重合体ゴム(A)100重量部に対し、好ましくは5~120重量部、より好ましくは10~110重量部、さらに好ましくは20~100重量部、さらにより好ましくは25~80重量部、特に好ましくは40~70重量部である。塩化ビニル樹脂(B)の含有量を上記範囲とすることにより、得られるゴム架橋物の耐寒性をより良好なものとしながら、耐オゾン性、耐燃料油膨潤性、および耐燃料油透過性をより高めることができる。
The content of the vinyl chloride resin (B) in the nitrile rubber composition of the present invention is preferably 5 to 120 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the nitrile group-containing copolymer rubber (A). The amount is 110 parts by weight, more preferably 20 to 100 parts by weight, still more preferably 25 to 80 parts by weight, particularly preferably 40 to 70 parts by weight. By setting the content of the vinyl chloride resin (B) within the above range, the obtained rubber crosslinked product has better cold resistance, and has improved ozone resistance, fuel oil swelling resistance, and fuel oil permeability. Can be more enhanced.
<可塑剤(C)>
本発明のニトリルゴム組成物は、上述したニトリル基含有共重合体ゴム(A)および塩化ビニル樹脂(B)に加えて、分子量が500~2000である可塑剤(C)を含有する。分子量が500~2000である可塑剤(C)(以下、適宜、「可塑剤(C)」とする。)を、上述したニトリル基含有共重合体ゴム(A)および塩化ビニル樹脂(B)を組み合わせて用いることで、硬くなることにより加工性が低下してしまうことを有効に防止でき、これにより、ニトリルゴム組成物を優れた加工性を有するものとすることができ、しかも、得られるゴム架橋物を、耐圧縮永久歪み性、圧縮応力保持率および耐寒性に優れたものとすることができるものである。また、本発明においては、上述したニトリル基含有共重合体ゴム(A)および塩化ビニル樹脂(B)を用いるものであるため、これらに由来する効果、すなわち、得られるゴム架橋物を耐燃料油膨潤性、耐燃料油透過性、耐オゾン性および耐熱性に優れたものとすることができるという効果をも奏することができるものである。特に、本発明によれば、得られるゴム架橋物を、耐圧縮永久歪み性に加え、圧縮応力保持率にも優れるものとすることができるため、圧縮して用いられる用途、特に金属接合部品とゴム架橋物との加締め部分を有する燃料ホース用途などに好適に用いることができる。 <Plasticizer (C)>
The nitrile rubber composition of the present invention contains a plasticizer (C) having a molecular weight of 500 to 2,000 in addition to the nitrile group-containing copolymer rubber (A) and the vinyl chloride resin (B). The plasticizer (C) having a molecular weight of 500 to 2,000 (hereinafter, appropriately referred to as “plasticizer (C)”) is used as the above-mentioned nitrile group-containing copolymer rubber (A) and vinyl chloride resin (B). By using in combination, it is possible to effectively prevent the workability from being lowered due to being hardened, whereby the nitrile rubber composition can have excellent workability, and furthermore, the obtained rubber The crosslinked product can be made excellent in compression set resistance, compression stress retention and cold resistance. Further, in the present invention, since the above-mentioned nitrile group-containing copolymer rubber (A) and vinyl chloride resin (B) are used, the effects derived from them, that is, the obtained rubber cross-linked product is used as a fuel-resistant oil It also has the effect of being able to have excellent swelling properties, fuel oil permeability, ozone resistance and heat resistance. In particular, according to the present invention, the obtained rubber cross-linked product, in addition to compression set resistance, can also be excellent in compressive stress retention, so that it can be used for compression, particularly for metal-bonded parts. It can be suitably used for fuel hose applications having a crimped portion with a rubber crosslinked product.
本発明のニトリルゴム組成物は、上述したニトリル基含有共重合体ゴム(A)および塩化ビニル樹脂(B)に加えて、分子量が500~2000である可塑剤(C)を含有する。分子量が500~2000である可塑剤(C)(以下、適宜、「可塑剤(C)」とする。)を、上述したニトリル基含有共重合体ゴム(A)および塩化ビニル樹脂(B)を組み合わせて用いることで、硬くなることにより加工性が低下してしまうことを有効に防止でき、これにより、ニトリルゴム組成物を優れた加工性を有するものとすることができ、しかも、得られるゴム架橋物を、耐圧縮永久歪み性、圧縮応力保持率および耐寒性に優れたものとすることができるものである。また、本発明においては、上述したニトリル基含有共重合体ゴム(A)および塩化ビニル樹脂(B)を用いるものであるため、これらに由来する効果、すなわち、得られるゴム架橋物を耐燃料油膨潤性、耐燃料油透過性、耐オゾン性および耐熱性に優れたものとすることができるという効果をも奏することができるものである。特に、本発明によれば、得られるゴム架橋物を、耐圧縮永久歪み性に加え、圧縮応力保持率にも優れるものとすることができるため、圧縮して用いられる用途、特に金属接合部品とゴム架橋物との加締め部分を有する燃料ホース用途などに好適に用いることができる。 <Plasticizer (C)>
The nitrile rubber composition of the present invention contains a plasticizer (C) having a molecular weight of 500 to 2,000 in addition to the nitrile group-containing copolymer rubber (A) and the vinyl chloride resin (B). The plasticizer (C) having a molecular weight of 500 to 2,000 (hereinafter, appropriately referred to as “plasticizer (C)”) is used as the above-mentioned nitrile group-containing copolymer rubber (A) and vinyl chloride resin (B). By using in combination, it is possible to effectively prevent the workability from being lowered due to being hardened, whereby the nitrile rubber composition can have excellent workability, and furthermore, the obtained rubber The crosslinked product can be made excellent in compression set resistance, compression stress retention and cold resistance. Further, in the present invention, since the above-mentioned nitrile group-containing copolymer rubber (A) and vinyl chloride resin (B) are used, the effects derived from them, that is, the obtained rubber cross-linked product is used as a fuel-resistant oil It also has the effect of being able to have excellent swelling properties, fuel oil permeability, ozone resistance and heat resistance. In particular, according to the present invention, the obtained rubber cross-linked product, in addition to compression set resistance, can also be excellent in compressive stress retention, so that it can be used for compression, particularly for metal-bonded parts. It can be suitably used for fuel hose applications having a crimped portion with a rubber crosslinked product.
可塑剤(C)としては、分子量が500~2000の範囲にあるものであればよく、特に限定されないが、得られるゴム架橋物の圧縮応力保持率をより高めることができるという観点より、下記一般式(1)で表されるポリエーテルエステル(c1)、または、分子量が800~2000であり、温度25℃における粘度が50~1500mPa・sであるアジピン酸系ポリエステル(c2)が好ましい。
The plasticizer (C) is not particularly limited as long as it has a molecular weight in the range of 500 to 2,000. From the viewpoint that the obtained rubber cross-linked product can further increase the compressive stress retention, The polyetherester (c1) represented by the formula (1) or the adipic acid-based polyester (c2) having a molecular weight of 800 to 2,000 and a viscosity at 25 ° C. of 50 to 1500 mPa · s is preferable.
上記一般式(1)中、R1は、それぞれ独立して、水素原子、または炭素数1~20の炭化水素基であり、好ましくは水素原子、または炭素数1~15の炭化水素基であり、特に好ましくは、炭素数1~10の炭化水素基である。また、上記一般式(1)中、R2は、それぞれ独立して、水素原子、または炭素数1~8の炭化水素基であり、好ましくは水素原子、または炭素数1~7の炭化水素基であり、より好ましくは水素原子である。また、上記一般式(1)中、nは1~40の整数であり、好ましくは2~30の整数、より好ましくは3~30の整数である。
In the general formula (1), R 1 is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms. Particularly preferred is a hydrocarbon group having 1 to 10 carbon atoms. In the general formula (1), R 2 is each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms. And more preferably a hydrogen atom. In the above general formula (1), n is an integer of 1 to 40, preferably an integer of 2 to 30, and more preferably an integer of 3 to 30.
なお、上記一般式(1)で表されるポリエーテルエステル(c1)は、たとえば、対応するアルキレンオキサイドの重合体を得て、得られた重合体の末端水酸基と、対応するカルボン酸を反応させることで、エステル化することにより製造することができる。
For the polyetherester (c1) represented by the general formula (1), for example, a corresponding alkylene oxide polymer is obtained, and a terminal hydroxyl group of the obtained polymer is reacted with a corresponding carboxylic acid. Thus, it can be produced by esterification.
また、上記一般式(1)で表されるポリエーテルエステル(c1)としては、得られるゴム架橋物の圧縮応力保持率をより高めることができるという観点より、分子量が500~1200の範囲にあるものがより好ましく、分子量が520~900の範囲にあるものがさらに好ましい。また、同様に、得られるゴム架橋物の圧縮応力保持率をより高めることができるという観点より、上記一般式(1)で表されるポリエーテルエステル(c1)としては、温度25℃における粘度が15~300mPa・sの範囲にあるものが好ましく、22~150mPa・sの範囲にあるものがより好ましく、25~100mPa・sの範囲にあるものが特に好ましい。また、上記一般式(1)で表されるポリエーテルエステル(c1)としては、引火点が216~300℃の範囲にあるものが好ましく、引火点が220~260℃の範囲にあるものがより好ましい。
Further, the molecular weight of the polyetherester (c1) represented by the general formula (1) is in the range of 500 to 1200 from the viewpoint that the obtained rubber crosslinked product can have a higher compressive stress retention. Those having a molecular weight in the range of 520 to 900 are more preferable. Similarly, from the viewpoint that the obtained rubber cross-linked product can further increase the compressive stress retention, the polyetherester (c1) represented by the general formula (1) has a viscosity at a temperature of 25 ° C. Those in the range of 15 to 300 mPa · s are preferable, those in the range of 22 to 150 mPa · s are more preferable, and those in the range of 25 to 100 mPa · s are particularly preferable. As the polyetherester (c1) represented by the general formula (1), those having a flash point in the range of 216 to 300 ° C. are preferable, and those having a flash point in the range of 220 to 260 ° C. are more preferable. preferable.
あるいは、可塑剤(C)としては、分子量が800~2000であり、温度25℃における粘度が50~1500mPa・sであるアジピン酸系ポリエステル(c2)(以下、適宜、「アジピン酸系ポリエステル(c2)」とする。)も好適に用いることができ、アジピン酸系ポリエステル(c2)としては、分子量および温度25℃における粘度が上記範囲にある、ジカルボン酸であるアジピン酸とアルコールとの反応物であればよく特に限定されない。アジピン酸系ポリエステル(c2)としては、たとえば、アジピン酸および多価アルコールとの反応物や、アジピン酸および多価アルコールに加えて、1価アルコールまたは1価カルボン酸をさらに反応させたものであってもよい。
Alternatively, as the plasticizer (C), an adipic acid-based polyester (c2) having a molecular weight of 800 to 2,000 and a viscosity at a temperature of 25 ° C. of 50 to 1500 mPa · s (hereinafter referred to as “adipic acid-based polyester (c2 ) ") Is also preferably used. As the adipic acid-based polyester (c2), a reaction product of an adipic acid, which is a dicarboxylic acid, and an alcohol having a molecular weight and a viscosity at a temperature of 25 ° C. within the above ranges is used. There is no particular limitation as long as it exists. The adipic acid-based polyester (c2) is, for example, a reaction product of adipic acid and a polyhydric alcohol, or a product obtained by further reacting a monohydric alcohol or a monocarboxylic acid in addition to adipic acid and a polyhydric alcohol. You may.
2価アルコールとしては、エチレングリコール、プロピレングリコール、プタンジオール、1.6-ヘキサンジオールなどが挙げられる。1価アルコールとしては、ノナノール、デカノール、ウンデカノール、ドデカノール、トリデカノール、テトラデカノール、ヘキサデカノール、オクタデカノールなどが挙げられる。また、1価カルボン酸としては、ノナン酸、カプリン酸、ウンデシル酸、ラウリン酸などが挙げられる。
Examples of the dihydric alcohol include ethylene glycol, propylene glycol, butanediol, 1.6-hexanediol and the like. Examples of the monohydric alcohol include nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, hexadecanol, octadecanol and the like. Examples of the monovalent carboxylic acid include nonanoic acid, capric acid, undecylic acid, and lauric acid.
アジピン酸系ポリエステル(c2)としては、分子量が800~2000であり、温度25℃における粘度が50~1500mPa・sであるものであればよいが、得られるゴム架橋物の圧縮応力保持率をより高めることができるという観点より、分子量が900~1600の範囲にあるものが好ましく、分子量が1000~1300の範囲にあるものがより好ましい。また、得られるゴム架橋物の圧縮応力保持率をより高めることができるという観点より、温度25℃における粘度が500~1200mPa・sの範囲にあるものが好ましく、650~1000mPa・sの範囲にあるものがより好ましい。また、アジピン酸系ポリエステル(c2)としては、引火点が216~300℃の範囲にあるものが好ましく、引火点が220~260℃の範囲にあるものがより好ましい。
The adipic acid-based polyester (c2) may be any polyester having a molecular weight of 800 to 2,000 and a viscosity at a temperature of 25 ° C. of 50 to 1500 mPa · s. From the viewpoint that the molecular weight can be increased, those having a molecular weight in the range of 900 to 1600 are preferable, and those having a molecular weight in the range of 1000 to 1300 are more preferable. Further, from the viewpoint that the obtained rubber cross-linked product can further increase the compressive stress retention, the viscosity at a temperature of 25 ° C. is preferably in the range of 500 to 1200 mPa · s, and more preferably in the range of 650 to 1000 mPa · s. Are more preferred. As the adipic acid-based polyester (c2), those having a flash point in the range of 216 to 300 ° C. are preferable, and those having a flash point in the range of 220 to 260 ° C. are more preferable.
なお、可塑剤(C)としては、一種を単独で用いてもよく、二種以上を併用してもよい。たとえば、可塑剤(C)として、二種以上を併用する場合には、二種以上の上記一般式(1)で表されるポリエーテルエステル(c1)を用いてもよいし、二種以上のアジピン酸系ポリエステル(c2)を用いてもよいし、さらには、上記一般式(1)で表されるポリエーテルエステル(c1)と、アジピン酸系ポリエステル(c2)とを組み合わせて用いてもよい。
As the plasticizer (C), one type may be used alone, or two or more types may be used in combination. For example, when two or more kinds are used in combination as the plasticizer (C), two or more kinds of polyetheresters (c1) represented by the above general formula (1) may be used, or two or more kinds may be used. The adipic acid-based polyester (c2) may be used, or a combination of the polyetherester (c1) represented by the general formula (1) and the adipic acid-based polyester (c2) may be used. .
本発明のニトリルゴム組成物中における、可塑剤(C)の含有量は、ニトリル基含有共重合体ゴム(A)100重量部に対し、好ましくは1~60重量部、より好ましくは3~55重量部、さらに好ましくは5~50重量部であり、さらにより好ましくは8~40重量部であり、特に好ましくは10~40重量部であり、最も好ましくは15~30重量部である。可塑剤(C)の含有量を上記範囲とすることにより、ブリードの発生を抑制しながら、得られるゴム架橋物の圧縮応力保持率をより高めることができる。
The content of the plasticizer (C) in the nitrile rubber composition of the present invention is preferably 1 to 60 parts by weight, more preferably 3 to 55 parts by weight, based on 100 parts by weight of the nitrile group-containing copolymer rubber (A). Parts by weight, more preferably 5 to 50 parts by weight, even more preferably 8 to 40 parts by weight, particularly preferably 10 to 40 parts by weight, most preferably 15 to 30 parts by weight. By setting the content of the plasticizer (C) in the above range, it is possible to further increase the compressive stress retention of the obtained cross-linked rubber while suppressing the occurrence of bleed.
<安定剤>
また、本発明のニトリルゴム組成物は、安定剤をさらに含有していることが好ましい。安定剤としては、塩化ビニル樹脂の安定剤として作用する化合物であればよく、特に限定されず、カルシウム-亜鉛系安定剤、カルシウム-マグネシウム-亜鉛系安定剤、バリウム-亜鉛系安定剤、スズ系安定剤、鉛系安定剤、ハイドロタルサイト系安定剤、ゼオライト系安定剤などが挙げられるが、これらのなかでも、カルシウム-マグネシウム-亜鉛系安定剤、ハイドロタルサイト系安定剤が好ましく、カルシウム-マグネシウム-亜鉛系安定剤がより好ましい。 <Stabilizer>
Further, the nitrile rubber composition of the present invention preferably further contains a stabilizer. The stabilizer may be any compound that acts as a stabilizer for the vinyl chloride resin, and is not particularly limited. Calcium-zinc stabilizer, calcium-magnesium-zinc stabilizer, barium-zinc stabilizer, tin-based stabilizer Examples include stabilizers, lead stabilizers, hydrotalcite stabilizers, and zeolite stabilizers. Of these, calcium-magnesium-zinc stabilizers and hydrotalcite stabilizers are preferred. Magnesium-zinc stabilizers are more preferred.
また、本発明のニトリルゴム組成物は、安定剤をさらに含有していることが好ましい。安定剤としては、塩化ビニル樹脂の安定剤として作用する化合物であればよく、特に限定されず、カルシウム-亜鉛系安定剤、カルシウム-マグネシウム-亜鉛系安定剤、バリウム-亜鉛系安定剤、スズ系安定剤、鉛系安定剤、ハイドロタルサイト系安定剤、ゼオライト系安定剤などが挙げられるが、これらのなかでも、カルシウム-マグネシウム-亜鉛系安定剤、ハイドロタルサイト系安定剤が好ましく、カルシウム-マグネシウム-亜鉛系安定剤がより好ましい。 <Stabilizer>
Further, the nitrile rubber composition of the present invention preferably further contains a stabilizer. The stabilizer may be any compound that acts as a stabilizer for the vinyl chloride resin, and is not particularly limited. Calcium-zinc stabilizer, calcium-magnesium-zinc stabilizer, barium-zinc stabilizer, tin-based stabilizer Examples include stabilizers, lead stabilizers, hydrotalcite stabilizers, and zeolite stabilizers. Of these, calcium-magnesium-zinc stabilizers and hydrotalcite stabilizers are preferred. Magnesium-zinc stabilizers are more preferred.
本発明のニトリルゴム組成物中における、安定剤の含有量は、塩化ビニル樹脂(B)100重量部に対し、好ましくは1~50重量部、より好ましくは2~45重量部、さらに好ましくは5~45重量部である。安定剤の含有量を上記範囲とすることにより、色調の悪化を有効に抑制しながら、塩化ビニル樹脂(B)の安定化効果を十分なものとすることができる。
The content of the stabilizer in the nitrile rubber composition of the present invention is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts by weight, further preferably 5 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin (B). 4545 parts by weight. By setting the content of the stabilizer within the above range, the effect of stabilizing the vinyl chloride resin (B) can be made sufficient while effectively suppressing the deterioration of the color tone.
<配合剤>
また、本発明のニトリルゴム組成物は、ゴム分野において用いられる各種配合剤を含有していてもよい。このような配合剤としては、代表的には、充填剤が挙げられる。 <Compounding agent>
Further, the nitrile rubber composition of the present invention may contain various compounding agents used in the rubber field. Such a compounding agent typically includes a filler.
また、本発明のニトリルゴム組成物は、ゴム分野において用いられる各種配合剤を含有していてもよい。このような配合剤としては、代表的には、充填剤が挙げられる。 <Compounding agent>
Further, the nitrile rubber composition of the present invention may contain various compounding agents used in the rubber field. Such a compounding agent typically includes a filler.
充填剤としては、カーボンブラックや、シリカ、炭酸カルシウム、珪酸アルミニウム、珪酸マグネシウム、珪酸カルシウム、酸化マグネシウム、短繊維、(メタ)アクリル酸亜鉛や(メタ)アクリル酸マグネシウムなどのα,β-エチレン性不飽和カルボン酸金属塩などが挙げられる。これらのなかでも、機械的強度をより高めることができるという観点より、カーボンブラックおよびシリカが好ましく、カーボンブラックがより好ましい。なお、充填剤としては、その表面を表面処理剤などで表面処理されたものを用いてもよい。
Fillers include α, β-ethylenic substances such as carbon black, silica, calcium carbonate, aluminum silicate, magnesium silicate, calcium silicate, magnesium oxide, short fibers, zinc (meth) acrylate and magnesium (meth) acrylate. And unsaturated carboxylic acid metal salts. Among them, carbon black and silica are preferred, and carbon black is more preferred, from the viewpoint that the mechanical strength can be further increased. As the filler, a filler whose surface is surface-treated with a surface treatment agent or the like may be used.
カーボンブラックとしては、特に限定されないが、たとえば、ファーネスブラック、アセチレンブラック、サーマルブラック、チャンネルブラック、グラファイトなどが挙げられる。これらのなかでも、ファーネスブラックを用いることが好ましく、その具体例としては、SAF、ISAF、ISAF-HS、ISAF-LS、HAF、HAF-HS、HAF-LS、FEF、SRF、FT、MTなどが挙げられる。これらは、一種を単独で用いてもよく、二種以上を併用してもよい。
Carbon black is not particularly limited, but examples thereof include furnace black, acetylene black, thermal black, channel black, and graphite. Among these, furnace black is preferably used, and specific examples thereof include SAF, ISAF, ISAF-HS, ISAF-LS, HAF, HAF-HS, HAF-LS, FEF, SRF, FT, and MT. No. These may be used alone or in combination of two or more.
シリカとしては、特に限定されないが、たとえば、乾式法ホワイトカーボン、湿式法ホワイトカーボン、コロイダルシリカ、沈降シリカ、表面処理シリカなどを用いることができる。また、カーボンブラック表面にシリカを担持させたカーボン-シリカ デュアル・フェイズ・フィラーを用いてもよい。
Silica is not particularly limited, but for example, dry-process white carbon, wet-process white carbon, colloidal silica, precipitated silica, surface-treated silica, and the like can be used. Alternatively, a carbon-silica dual phase filler having silica supported on the surface of carbon black may be used.
本発明のニトリルゴム組成物中における、充填剤の含有量は、ニトリル基含有共重合体ゴム(A)100重量部に対し、好ましくは10~80重量部、より好ましくは15~75重量部、さらに好ましくは20~70重量部である。充填剤の含有量を上記範囲とすることにより、ニトリルゴム組成物の加工性を良好に保ちながら、得られるゴム架橋物の機械的強度を適切に高めることができる。
The content of the filler in the nitrile rubber composition of the present invention is preferably 10 to 80 parts by weight, more preferably 15 to 75 parts by weight, based on 100 parts by weight of the nitrile group-containing copolymer rubber (A). More preferably, the amount is 20 to 70 parts by weight. By setting the content of the filler within the above range, the mechanical strength of the rubber cross-linked product obtained can be appropriately increased while maintaining good processability of the nitrile rubber composition.
また、本発明のニトリルゴム組成物は、さらに架橋剤を含有していることが好ましく、架橋剤を含有させることにより、本発明のニトリルゴム組成物を、架橋性の組成物、すなわち、架橋性ニトリルゴム組成物とすることができる。
Further, the nitrile rubber composition of the present invention preferably further contains a cross-linking agent. By adding a cross-linking agent, the nitrile rubber composition of the present invention becomes a cross-linkable composition, It can be a nitrile rubber composition.
架橋剤としては、特に限定されないが、たとえば、硫黄系架橋剤、有機過酸化物架橋剤などが挙げられるが、これらのなかでも、硫黄系架橋剤が好ましい。
硫黄系架橋剤としては、粉末硫黄、硫黄華、沈降性硫黄、コロイド硫黄、表面処理硫黄、不溶性硫黄などの硫黄;塩化硫黄、二塩化硫黄、4,4’-ジチオジモルホリン、4,4’-テトラチオジモルホリン、モルホリノジチオ蟻酸4-モルホリニル、アルキルフェノールジスルフィド、ジベンゾチアジルジスルフィド、カプロラクタムジスルフィド、含リンポリスルフィド、高分子多硫化物などの含硫黄化合物;テトラメチルチウラムジスルフィド、ジメチルジチオカルバミン酸セレンなどの硫黄供与性化合物;などが挙げられる。これらのなかでも、得られる架橋性のゴム組成物を、架橋安定性により優れたものとすることができるという点より、4,4’-ジチオジモルホリン、4,4’-テトラチオジモルホリン、モルホリノジチオ蟻酸4-モルホリニルなどのモルホリン構造を有する含硫黄化合物が好ましく、4,4’-ジチオジモルホリンが特に好ましい。 The crosslinking agent is not particularly limited, and includes, for example, a sulfur-based crosslinking agent and an organic peroxide crosslinking agent. Among these, a sulfur-based crosslinking agent is preferred.
Sulfur-based crosslinking agents include sulfur such as powdered sulfur, sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur and insoluble sulfur; sulfur chloride, sulfur dichloride, 4,4′-dithiodimorpholine, and 4,4 ′ -Sulfur-containing compounds such as tetrathiodimorpholine, 4-morpholinyl morpholinodithiothioate, alkylphenol disulfide, dibenzothiazyl disulfide, caprolactam disulfide, phosphorus-containing polysulfide, and high molecular polysulfide; tetramethylthiuram disulfide, selenium dimethyldithiocarbamate Sulfur donating compounds; and the like. Among them, 4,4′-dithiodimorpholine, 4,4′-tetrathiodimorpholine, from the viewpoint that the obtained crosslinkable rubber composition can be more excellent in crosslink stability. Sulfur-containing compounds having a morpholine structure such as 4-morpholinyl morpholinodithioformate are preferred, and 4,4'-dithiodimorpholine is particularly preferred.
硫黄系架橋剤としては、粉末硫黄、硫黄華、沈降性硫黄、コロイド硫黄、表面処理硫黄、不溶性硫黄などの硫黄;塩化硫黄、二塩化硫黄、4,4’-ジチオジモルホリン、4,4’-テトラチオジモルホリン、モルホリノジチオ蟻酸4-モルホリニル、アルキルフェノールジスルフィド、ジベンゾチアジルジスルフィド、カプロラクタムジスルフィド、含リンポリスルフィド、高分子多硫化物などの含硫黄化合物;テトラメチルチウラムジスルフィド、ジメチルジチオカルバミン酸セレンなどの硫黄供与性化合物;などが挙げられる。これらのなかでも、得られる架橋性のゴム組成物を、架橋安定性により優れたものとすることができるという点より、4,4’-ジチオジモルホリン、4,4’-テトラチオジモルホリン、モルホリノジチオ蟻酸4-モルホリニルなどのモルホリン構造を有する含硫黄化合物が好ましく、4,4’-ジチオジモルホリンが特に好ましい。 The crosslinking agent is not particularly limited, and includes, for example, a sulfur-based crosslinking agent and an organic peroxide crosslinking agent. Among these, a sulfur-based crosslinking agent is preferred.
Sulfur-based crosslinking agents include sulfur such as powdered sulfur, sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur and insoluble sulfur; sulfur chloride, sulfur dichloride, 4,4′-dithiodimorpholine, and 4,4 ′ -Sulfur-containing compounds such as tetrathiodimorpholine, 4-morpholinyl morpholinodithiothioate, alkylphenol disulfide, dibenzothiazyl disulfide, caprolactam disulfide, phosphorus-containing polysulfide, and high molecular polysulfide; tetramethylthiuram disulfide, selenium dimethyldithiocarbamate Sulfur donating compounds; and the like. Among them, 4,4′-dithiodimorpholine, 4,4′-tetrathiodimorpholine, from the viewpoint that the obtained crosslinkable rubber composition can be more excellent in crosslink stability. Sulfur-containing compounds having a morpholine structure such as 4-morpholinyl morpholinodithioformate are preferred, and 4,4'-dithiodimorpholine is particularly preferred.
本発明のニトリルゴム組成物(架橋性ニトリルゴム組成物)中における、架橋剤の含有量は、ニトリル基含有共重合体ゴム(A)100重量部に対し、好ましくは0.1~10重量部、より好ましくは0.2~8重量部、さらに好ましくは0.5~6重量部である。架橋剤の含有量を上記範囲とすることにより、架橋安定性を良好なものとしながら、得られるゴム架橋物の機械的特性をより良好なものとすることができる。
The content of the crosslinking agent in the nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the nitrile group-containing copolymer rubber (A). , More preferably 0.2 to 8 parts by weight, even more preferably 0.5 to 6 parts by weight. By setting the content of the crosslinking agent in the above range, it is possible to improve the mechanical properties of the obtained rubber cross-linked product while improving the cross-linking stability.
また、上記した硫黄系架橋剤を用いる場合には、活性亜鉛華、亜鉛華、カルシウム-マグネシウム-亜鉛系化合物などの亜鉛含有化合物、ステアリン酸などの架橋助剤;グアニジン系、チウラム系、アルデヒド-アミン系、アルデヒド-アンモニア系、チアゾール系、スルフェンアミド系、チオ尿素系などの架橋促進剤;を併用することが好ましい。これらの架橋助剤および架橋促進剤の使用量は、ニトリル共重合体ゴム(A)100重量部に対して、好ましくは0.1~20重量部の範囲である。
When the above-mentioned sulfur-based cross-linking agent is used, activated zinc white, zinc white, zinc-containing compounds such as calcium-magnesium-zinc-based compounds, cross-linking assistants such as stearic acid; guanidine-based, thiuram-based, aldehyde- It is preferable to use an amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, or thiourea-based crosslinking accelerator; The amount of these crosslinking aids and crosslinking accelerators used is preferably in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the nitrile copolymer rubber (A).
さらに、本発明のニトリルゴム組成物(架橋性ニトリルゴム組成物)には、上記以外の配合剤、たとえば、架橋遅延剤、老化防止剤、補強剤、滑剤、粘着剤、潤滑剤、加工助剤、難燃剤、防黴剤、帯電防止剤、着色剤などの添加剤を配合してもよい。
Further, the nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention may contain other additives such as a crosslinking retarder, an antioxidant, a reinforcing agent, a lubricant, an adhesive, a lubricant, and a processing aid. And additives such as a flame retardant, a fungicide, an antistatic agent, and a coloring agent.
さらに、本発明のニトリルゴム組成物(架橋性ニトリルゴム組成物)には、本発明の効果が阻害されない範囲で、配合剤として、上記ニトリル基含有共重合体ゴム(A)以外のゴムを配合してもよい。ニトリル基含有共重合体ゴム(A)以外のゴムとしては、アクリルゴム、エチレン-アクリル酸共重合体ゴム、フッ素ゴム、スチレン-ブタジエン共重合体ゴム、ポリブタジエンゴム、エチレン-プロピレン共重合体ゴム、エチレン-プロピレン-ジエン三元共重合体ゴム、エピクロロヒドリンゴム、ウレタンゴム、クロロプレンゴム、シリコーンゴム、フルオロシリコーンゴム、クロロスルフォン化ポリエチレンゴム、天然ゴムおよびポリイソプレンゴムなどを挙げることができる。ニトリル基含有共重合体ゴム(A)以外のゴムを配合する場合における配合量は、ニトリル基含有共重合体ゴム(A)100重量部に対して、30重量部以下が好ましく、20重量部以下がより好ましく、10重量部以下が特に好ましい。
Further, the nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention contains a rubber other than the nitrile group-containing copolymer rubber (A) as a compounding agent as long as the effects of the present invention are not impaired. May be. Examples of the rubber other than the nitrile group-containing copolymer rubber (A) include acrylic rubber, ethylene-acrylic acid copolymer rubber, fluororubber, styrene-butadiene copolymer rubber, polybutadiene rubber, ethylene-propylene copolymer rubber, Examples include ethylene-propylene-diene terpolymer rubber, epichlorohydrin rubber, urethane rubber, chloroprene rubber, silicone rubber, fluorosilicone rubber, chlorosulfonated polyethylene rubber, natural rubber, and polyisoprene rubber. When compounding a rubber other than the nitrile group-containing copolymer rubber (A), the compounding amount is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the nitrile group-containing copolymer rubber (A). And more preferably 10 parts by weight or less.
本発明のニトリルゴム組成物(架橋性ニトリルゴム組成物)のコンパウンド・ムーニー粘度(ML1+4、100℃)は、好ましくは20~150、より好ましくは30~120、さらに好ましくは40~100である。本発明よれば、分子量が500~2000である可塑剤(C)を配合するものであるため、ニトリル基含有共重合体ゴムとして、上述したように、α,β-エチレン性不飽和ニトリル単量体単位が比較的高く、ヨウ素価が比較的低いニトリル基含有共重合体ゴム(A)を用いた場合でも、上記のようにコンパウンド・ムーニー粘度が低く抑えられ、加工性に優れたものとすることができるものである。
The compound Mooney viscosity (ML1 + 4, 100 ° C.) of the nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention is preferably 20 to 150, more preferably 30 to 120, and further preferably 40 to 100. According to the present invention, since a plasticizer (C) having a molecular weight of 500 to 2,000 is compounded, as described above, the α, β-ethylenically unsaturated nitrile monopolymer is used as a nitrile group-containing copolymer rubber. Even when the nitrile group-containing copolymer rubber (A) having a relatively high body unit and a relatively low iodine value is used, the compound Mooney viscosity is suppressed to a low level as described above, and the workability is excellent. Is what you can do.
<ニトリルゴム組成物、架橋性ニトリルゴム組成物の製造方法>
本発明のニトリルゴム組成物(架橋性ニトリルゴム組成物)は、上述したニトリル基含有共重合体ゴム(A)と、塩化ビニル樹脂(B)と、可塑剤(C)とを混合することにより製造することができる。 <Method for producing nitrile rubber composition and crosslinkable nitrile rubber composition>
The nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention is obtained by mixing the above-described nitrile group-containing copolymer rubber (A), vinyl chloride resin (B), and plasticizer (C). Can be manufactured.
本発明のニトリルゴム組成物(架橋性ニトリルゴム組成物)は、上述したニトリル基含有共重合体ゴム(A)と、塩化ビニル樹脂(B)と、可塑剤(C)とを混合することにより製造することができる。 <Method for producing nitrile rubber composition and crosslinkable nitrile rubber composition>
The nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention is obtained by mixing the above-described nitrile group-containing copolymer rubber (A), vinyl chloride resin (B), and plasticizer (C). Can be manufactured.
また、本発明のニトリルゴム組成物(架橋性ニトリルゴム組成物)を、充填剤や架橋剤などの配合剤を含有するものとする場合には、次のような工程を採用することが好ましい。
すなわち、ニトリルゴム組成物(架橋性ニトリルゴム組成物)中に含有させる可塑剤(C)の全量のうち一部を、ニトリル基含有共重合体ゴム(A)と、塩化ビニル樹脂(B)と混合する第1の混合工程と、
第1の混合工程において得られた組成物に、ニトリルゴム組成物(架橋性ニトリルゴム組成物)に含有させる可塑剤(C)の全量のうち残部と、配合剤とを配合し、混合する第2混合工程とを備えるものとすることが好ましい。 When the nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention contains a compounding agent such as a filler or a crosslinking agent, the following steps are preferably employed.
That is, a part of the total amount of the plasticizer (C) contained in the nitrile rubber composition (crosslinkable nitrile rubber composition) is partially converted into a nitrile group-containing copolymer rubber (A) and a vinyl chloride resin (B). A first mixing step of mixing;
In the composition obtained in the first mixing step, the rest of the total amount of the plasticizer (C) contained in the nitrile rubber composition (crosslinkable nitrile rubber composition) and a compounding agent are blended and mixed. It is preferable to include two mixing steps.
すなわち、ニトリルゴム組成物(架橋性ニトリルゴム組成物)中に含有させる可塑剤(C)の全量のうち一部を、ニトリル基含有共重合体ゴム(A)と、塩化ビニル樹脂(B)と混合する第1の混合工程と、
第1の混合工程において得られた組成物に、ニトリルゴム組成物(架橋性ニトリルゴム組成物)に含有させる可塑剤(C)の全量のうち残部と、配合剤とを配合し、混合する第2混合工程とを備えるものとすることが好ましい。 When the nitrile rubber composition (crosslinkable nitrile rubber composition) of the present invention contains a compounding agent such as a filler or a crosslinking agent, the following steps are preferably employed.
That is, a part of the total amount of the plasticizer (C) contained in the nitrile rubber composition (crosslinkable nitrile rubber composition) is partially converted into a nitrile group-containing copolymer rubber (A) and a vinyl chloride resin (B). A first mixing step of mixing;
In the composition obtained in the first mixing step, the rest of the total amount of the plasticizer (C) contained in the nitrile rubber composition (crosslinkable nitrile rubber composition) and a compounding agent are blended and mixed. It is preferable to include two mixing steps.
このように、ニトリルゴム組成物(架橋性ニトリルゴム組成物)中に含有させる可塑剤(C)の全量のうち一部を、ニトリル基含有共重合体ゴム(A)および塩化ビニル樹脂(B)と予め混合した後、充填剤や架橋剤などの配合剤を、残部の可塑剤(C)とともに添加し、混合する工程を採用することにより、可塑剤(C)のブリードを適切に抑制しながら、所望の量にて含有させることができるものである。具体的には、可塑剤(C)を、ニトリル基含有共重合体ゴム(A)100重量部に対し、好ましくは1~60重量部、より好ましくは3~55重量部、さらに好ましくは5~50重量部、さらにより好ましくは8~40重量部であり、特に好ましくは10~40重量部であり、最も好ましくは15~30重量部の範囲で含有させることができるものである。
As described above, a part of the total amount of the plasticizer (C) contained in the nitrile rubber composition (crosslinkable nitrile rubber composition) is converted to the nitrile group-containing copolymer rubber (A) and the vinyl chloride resin (B). After pre-mixing, a compounding agent such as a filler or a cross-linking agent is added together with the remaining plasticizer (C), and the process of mixing is employed to appropriately suppress bleeding of the plasticizer (C). , In a desired amount. Specifically, the plasticizer (C) is used in an amount of preferably 1 to 60 parts by weight, more preferably 3 to 55 parts by weight, and still more preferably 5 to 55 parts by weight, based on 100 parts by weight of the nitrile group-containing copolymer rubber (A). The amount can be 50 parts by weight, more preferably 8 to 40 parts by weight, particularly preferably 10 to 40 parts by weight, and most preferably 15 to 30 parts by weight.
この際においては、第1混合工程における可塑剤(C)の配合量を、ニトリルゴム組成物(架橋性ニトリルゴム組成物)中に含有させる可塑剤(C)の全量のうち、10~90重量%とすることが好ましく、20~90重量%とすることがより好ましく、25~85重量%とすることがさらに好ましく、55~75重量%とすることが特に好ましい。第1混合工程における可塑剤(C)の配合量を、このような割合とすることで、ブリードの発生を適切に防止しながら、生産効率をより高めることができる。
In this case, the blending amount of the plasticizer (C) in the first mixing step is 10 to 90% by weight of the total amount of the plasticizer (C) contained in the nitrile rubber composition (crosslinkable nitrile rubber composition). %, Preferably 20 to 90% by weight, more preferably 25 to 85% by weight, and particularly preferably 55 to 75% by weight. By setting the blending amount of the plasticizer (C) in such a ratio in the first mixing step, production efficiency can be further improved while appropriately preventing bleeding.
なお、第1混合工程における混合においては、第1混合工程において得られる組成物中の大部分が、ニトリル基含有共重合体ゴム(A)、塩化ビニル樹脂(B)、および可塑剤(C)から構成されているといえる割合、具体的には、これらの成分の合計の含有割合が、好ましくは95重量%以上、より好ましくは99重量%以上となるように混合することが好ましい。すなわち、好ましくは5重量%以下、より好ましくは1重量%以下であれば、安定剤などの配合剤等を含有するような態様としてもよい。
In the mixing in the first mixing step, most of the composition obtained in the first mixing step contains a nitrile group-containing copolymer rubber (A), a vinyl chloride resin (B), and a plasticizer (C). It is preferable that the components are mixed so that the ratio of these components, specifically, the total content of these components is preferably 95% by weight or more, more preferably 99% by weight or more. That is, when the content is preferably 5% by weight or less, more preferably 1% by weight or less, a mode may be adopted in which a compounding agent such as a stabilizer is contained.
第1混合工程における混合方法としては、特に限定されないが、ニトリル基含有共重合体ゴム(A)、塩化ビニル樹脂(B)、および可塑剤(C)をバンバリーミキサ、インターミキサ、ニーダ、ロールなどを用いて混練する方法などが挙げられる。第1混合工程における混合温度は、特に限定されないが、好ましくは40~200℃、より好ましくは50~190℃である。また、第1混合工程における混合時間も、特に限定されないが、好ましくは3~20分、より好ましくは5~15分である。
The mixing method in the first mixing step is not particularly limited, but the nitrile group-containing copolymer rubber (A), vinyl chloride resin (B), and plasticizer (C) can be mixed with a Banbury mixer, an intermixer, a kneader, a roll, or the like. And a method of kneading using the same. The mixing temperature in the first mixing step is not particularly limited, but is preferably from 40 to 200 ° C, more preferably from 50 to 190 ° C. Also, the mixing time in the first mixing step is not particularly limited, but is preferably 3 to 20 minutes, more preferably 5 to 15 minutes.
また、第2混合工程における混合方法としては、特に限定されないが、第1混合工程において得られた組成物、可塑剤(C)および充填剤や架橋剤などの配合剤を、バンバリーミキサ、インターミキサ、ニーダ、ロールなどで混合する方法が挙げられるが、この際においては、架橋剤や熱に不安定な成分(たとえば、架橋促進剤など)を除いた成分を、バンバリーミキサ、インターミキサ、ニーダなどの混合機で一次混合した後、ロールなどに移して架橋剤や熱に不安定な成分などを加えて二次混合する方法が好ましい。第2混合工程における混合温度(一次混合および二次混合における混合温度)は、特に限定されないが、好ましくは40~100℃、より好ましくは40~80℃である。また、第2混合工程における混合時間(一次混合および二次混合の合計の混合時間)も、特に限定されないが、好ましくは3~20分、より好ましくは3~15分である。
The mixing method in the second mixing step is not particularly limited, but the composition obtained in the first mixing step, the plasticizer (C), and the compounding agent such as a filler and a crosslinking agent are mixed with a Banbury mixer, an intermixer, and the like. , A kneader, a roll, or the like. In this case, a component excluding a crosslinking agent and a component unstable to heat (for example, a crosslinking accelerator) is replaced with a Banbury mixer, an intermixer, a kneader, or the like. The method of the present invention is preferably a method in which the mixture is primarily mixed by a mixer, and then transferred to a roll or the like, and a crosslinking agent or a component unstable to heat is added to the mixture to perform a secondary mixing. The mixing temperature in the second mixing step (the mixing temperature in the primary mixing and the secondary mixing) is not particularly limited, but is preferably 40 to 100 ° C, more preferably 40 to 80 ° C. Also, the mixing time (the total mixing time of the primary mixing and the secondary mixing) in the second mixing step is not particularly limited, but is preferably 3 to 20 minutes, more preferably 3 to 15 minutes.
<ゴム架橋物>
本発明のゴム架橋物は、上述した本発明の架橋性ニトリルゴム組成物(すなわち、本発明のニトリルゴム組成物に、架橋剤を配合してなる組成物)を架橋してなるものである。
本発明のゴム架橋物は、本発明の架橋性ニトリルゴム組成物を用い、所望の形状に対応した成形機、たとえば、押出機、射出成形機、圧縮機、ロールなどにより成形を行い、加熱することにより架橋反応を行い、架橋物として形状を固定化することにより製造することができる。この場合においては、予め成形した後に架橋しても、成形と同時に架橋を行ってもよい。成形温度は、通常、10~200℃、好ましくは25~120℃である。架橋温度は、通常、100~200℃、好ましくは130~190℃であり、架橋時間は、通常、1分~24時間、好ましくは2分~1時間である。 <Rubber crosslinked product>
The cross-linked rubber of the present invention is obtained by cross-linking the cross-linkable nitrile rubber composition of the present invention described above (that is, a composition obtained by blending a cross-linking agent with the nitrile rubber composition of the present invention).
The cross-linked rubber of the present invention is formed using the cross-linkable nitrile rubber composition of the present invention, and molded by a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll, and the like, and heated. Thus, a cross-linking reaction is carried out, and the shape can be fixed as a cross-linked product. In this case, crosslinking may be performed after molding in advance, or crosslinking may be performed simultaneously with molding. The molding temperature is usually from 10 to 200 ° C, preferably from 25 to 120 ° C. The crosslinking temperature is usually from 100 to 200 ° C., preferably from 130 to 190 ° C., and the crosslinking time is usually from 1 minute to 24 hours, preferably from 2 minutes to 1 hour.
本発明のゴム架橋物は、上述した本発明の架橋性ニトリルゴム組成物(すなわち、本発明のニトリルゴム組成物に、架橋剤を配合してなる組成物)を架橋してなるものである。
本発明のゴム架橋物は、本発明の架橋性ニトリルゴム組成物を用い、所望の形状に対応した成形機、たとえば、押出機、射出成形機、圧縮機、ロールなどにより成形を行い、加熱することにより架橋反応を行い、架橋物として形状を固定化することにより製造することができる。この場合においては、予め成形した後に架橋しても、成形と同時に架橋を行ってもよい。成形温度は、通常、10~200℃、好ましくは25~120℃である。架橋温度は、通常、100~200℃、好ましくは130~190℃であり、架橋時間は、通常、1分~24時間、好ましくは2分~1時間である。 <Rubber crosslinked product>
The cross-linked rubber of the present invention is obtained by cross-linking the cross-linkable nitrile rubber composition of the present invention described above (that is, a composition obtained by blending a cross-linking agent with the nitrile rubber composition of the present invention).
The cross-linked rubber of the present invention is formed using the cross-linkable nitrile rubber composition of the present invention, and molded by a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll, and the like, and heated. Thus, a cross-linking reaction is carried out, and the shape can be fixed as a cross-linked product. In this case, crosslinking may be performed after molding in advance, or crosslinking may be performed simultaneously with molding. The molding temperature is usually from 10 to 200 ° C, preferably from 25 to 120 ° C. The crosslinking temperature is usually from 100 to 200 ° C., preferably from 130 to 190 ° C., and the crosslinking time is usually from 1 minute to 24 hours, preferably from 2 minutes to 1 hour.
また、架橋物の形状、大きさなどによっては、表面が架橋していても内部まで十分に架橋していない場合があるので、さらに加熱して二次架橋を行ってもよい。
加熱方法としては、プレス加熱、スチーム加熱、オーブン加熱、熱風加熱などのゴムの架橋に用いられる一般的な方法を適宜選択すればよい。 In addition, depending on the shape and size of the crosslinked product, the surface may be crosslinked, but the inside may not be sufficiently crosslinked. Therefore, secondary crosslinking may be performed by further heating.
As a heating method, a general method used for rubber crosslinking, such as press heating, steam heating, oven heating, and hot air heating, may be appropriately selected.
加熱方法としては、プレス加熱、スチーム加熱、オーブン加熱、熱風加熱などのゴムの架橋に用いられる一般的な方法を適宜選択すればよい。 In addition, depending on the shape and size of the crosslinked product, the surface may be crosslinked, but the inside may not be sufficiently crosslinked. Therefore, secondary crosslinking may be performed by further heating.
As a heating method, a general method used for rubber crosslinking, such as press heating, steam heating, oven heating, and hot air heating, may be appropriately selected.
このようにして得られる本発明のゴム架橋物は、上述した本発明の架橋性ニトリルゴム組成物を用いて得られるものであり、上述したα,β-エチレン性不飽和ニトリル単量体単位が比較的高く、ヨウ素価が比較的低いニトリル基含有共重合体ゴム(A)と、塩化ビニル樹脂(B)とに由来する特性、すなわち、得られるゴム架橋物を耐燃料油膨潤性、耐燃料油透過性、耐オゾン性、および耐熱性に優れているという特性に加え、耐圧縮永久歪み性、圧縮応力保持率および耐寒性に優れるものである。このため、本発明のゴム架橋物は、このような特性を活かし、O-リング、パッキン、ダイアフラム、オイルシール、シャフトシール、ベアリングシール、ウェルヘッドシール、ショックアブソーバシール、空気圧機器用シール、エアコンディショナの冷却装置や空調装置の冷凍機用コンプレッサに使用されるフロン若しくはフルオロ炭化水素または二酸化炭素の密封用シール、精密洗浄の洗浄媒体に使用される超臨界二酸化炭素または亜臨界二酸化炭素の密封用シール、転動装置(転がり軸受、自動車用ハブユニット、自動車用ウォーターポンプ、リニアガイド装置およびボールねじ等)用のシール、バルブおよびバルブシート、BOP(Blow Out Preventer)、プラターなどの各種シール材;インテークマニホールドとシリンダヘッドとの連接部に装着されるインテークマニホールドガスケット、シリンダブロックとシリンダヘッドとの連接部に装着されるシリンダヘッドガスケット、ロッカーカバーとシリンダヘッドとの連接部に装着されるロッカーカバーガスケット、オイルパンとシリンダブロックあるいはトランスミッションケースとの連接部に装着されるオイルパンガスケット、正極、電解質板および負極を備えた単位セルを挟み込む一対のハウジング間に装着される燃料電池セパレーター用ガスケット、ハードディスクドライブのトップカバー用ガスケットなどの各種ガスケット;印刷用ロール、製鉄用ロール、製紙用ロール、工業用ロール、事務機用ロールなどの各種ロール;平ベルト(フィルムコア平ベルト、コード平ベルト、積層式平ベルト、単体式平ベルト等)、Vベルト(ラップドVベルト、ローエッジVベルト等)、Vリブドベルト(シングルVリブドベルト、ダブルVリブドベルト、ラップドVリブドベルト、背面ゴムVリブドベルト、上コグVリブドベルト等)、CVT用ベルト、タイミングベルト、歯付ベルト、コンベアーベルト、などの各種ベルト;燃料ホース、ターボエアーホース、オイルホース、ラジェターホース、ヒーターホース、ウォーターホース、バキュームブレーキホース、コントロールホース、エアコンホース、ブレーキホース、パワーステアリングホース、エアーホース、マリンホース、ライザー、フローラインなどの各種ホースなど幅広い用途に使用することができる。
The rubber cross-linked product of the present invention thus obtained is obtained by using the cross-linkable nitrile rubber composition of the present invention described above, wherein the α, β-ethylenically unsaturated nitrile monomer unit described above is used. The properties derived from the nitrile group-containing copolymer rubber (A) having a relatively high iodine value and the vinyl chloride resin (B), that is, the obtained rubber cross-linked product has a fuel oil swelling resistance and a fuel resistance. In addition to the properties of being excellent in oil permeability, ozone resistance and heat resistance, it has excellent compression set resistance, compressive stress retention and cold resistance. For this reason, the rubber crosslinked product of the present invention makes use of such characteristics and utilizes O-rings, packings, diaphragms, oil seals, shaft seals, bearing seals, well head seals, shock absorber seals, seals for pneumatic equipment, air conditioners, and the like. Sealing seal for chlorofluorocarbons, fluorohydrocarbons or carbon dioxide used in compressors for refrigerators and cooling units for air conditioners, sealing supercritical carbon dioxide or subcritical carbon dioxide used for cleaning media for precision cleaning Seals for rolling devices (rolling bearings, automotive hub units, automotive water pumps, linear guide devices, ball screws, etc.), valves and valve seats, various sealing materials such as BOP (Blow Out Preventer) and platters; Intake manifold and sieve Intake manifold gasket to be installed at the connection between cylinder head and cylinder head, cylinder head gasket to be installed at the connection between cylinder block and cylinder head, rocker cover gasket to be installed at the connection between rocker cover and cylinder head, oil pan Oil pan gasket to be attached to cylinder block or connection to transmission case, gasket for fuel cell separator to be fitted between a pair of housings sandwiching unit cell with positive electrode, electrolyte plate and negative electrode, for top cover of hard disk drive Various gaskets such as gaskets; various rolls such as printing rolls, steelmaking rolls, papermaking rolls, industrial rolls, and office machine rolls; flat belts (film core flat belts, cord flat belts, laminated flat belts, V-belt (single V-ribbed belt, double V-ribbed belt, double V-ribbed belt, wrapped V-ribbed belt, back rubber V-ribbed belt, upper cog V-ribbed belt, etc.), CVT belt, Various belts such as timing belts, toothed belts, conveyor belts, etc .; fuel hoses, turbo air hoses, oil hoses, radiator hoses, heater hoses, water hoses, vacuum brake hoses, control hoses, air conditioner hoses, brake hoses, power steering hoses It can be used for a wide range of applications such as various hoses such as air hoses, marine hoses, risers, and flow lines.
特に、本発明のゴム架橋物は、上述したα,β-エチレン性不飽和ニトリル単量体単位が比較的高く、ヨウ素価が比較的低いニトリル基含有共重合体ゴム(A)と、塩化ビニル樹脂(B)とに由来する特性、すなわち、得られるゴム架橋物を耐燃料油膨潤性、耐燃料油透過性、耐オゾン性および耐熱性に優れているという特性に加え、耐圧縮永久歪み性、圧縮応力保持率および耐寒性に優れるものであるため、燃料ホース用途に好適に用いることができ、たとえば、本発明のゴム架橋物からなる層を少なくとも1つの層とする2層以上の積層体からなる燃料ホースとして好適に用いることができる。なお、この際において、積層体を形成する他の層としては、フッ素ゴム、クロロプレンゴム、ヒドリンゴム、クロロスルホン化ポリエチレンゴム、アクリルゴム、エチレン-アクリル酸共重合体、エチレン-プロピレン共重合体、エチレン-プロピレン-ジエン3元共重合体、ブチルゴム、イソプレンゴム、天然ゴム、スチレン-ブタジエン共重合体、フッ素樹脂、ポリアミド樹脂、ポリビニルアルコール、エチレン-酢酸ビニル共重合樹脂、エチレン-ビニルアルコール共重合体樹脂、ポリブチレンナフタレート、ポリフェニレンスルフィド、ポリオレフィン樹脂、ポリエステル樹脂などが挙げられる。
In particular, the crosslinked rubber product of the present invention comprises a nitrile group-containing copolymer rubber (A) having a relatively high α, β-ethylenically unsaturated nitrile monomer unit and a relatively low iodine value, and vinyl chloride. In addition to the properties derived from the resin (B), that is, the resulting rubber cross-linked product is excellent in fuel oil swelling resistance, fuel oil permeation resistance, ozone resistance and heat resistance, as well as compression set resistance. Since it is excellent in compressive stress retention and cold resistance, it can be suitably used for fuel hose applications. For example, a laminate of two or more layers having at least one layer made of the crosslinked rubber of the present invention. It can be suitably used as a fuel hose made of In this case, the other layers forming the laminate include fluorine rubber, chloroprene rubber, hydrin rubber, chlorosulfonated polyethylene rubber, acrylic rubber, ethylene-acrylic acid copolymer, ethylene-propylene copolymer, ethylene -Propylene-diene terpolymer, butyl rubber, isoprene rubber, natural rubber, styrene-butadiene copolymer, fluororesin, polyamide resin, polyvinyl alcohol, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin , Polybutylene naphthalate, polyphenylene sulfide, polyolefin resin, polyester resin and the like.
以下に、実施例および比較例を挙げて、本発明についてより具体的に説明するが、本発明はこの実施例に限られるものではない。以下において、特記しない限り、「部」は重量基準である。物性および特性の試験または評価方法は以下のとおりである。
本 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following, “parts” are by weight unless otherwise specified. The methods for testing or evaluating physical properties and properties are as follows.
<ムーニー粘度(コンパウンド・ムーニー)>
架橋性ニトリルゴム組成物のムーニー粘度(コンパウンド・ムーニー)は、JIS K6300-1に従って測定した(単位は〔ML1+4、100℃〕)。 <Mooney viscosity (Compound Mooney)>
The Mooney viscosity (compound Mooney) of the crosslinkable nitrile rubber composition was measured according to JIS K6300-1 (unit: [ML1 + 4, 100 ° C.]).
架橋性ニトリルゴム組成物のムーニー粘度(コンパウンド・ムーニー)は、JIS K6300-1に従って測定した(単位は〔ML1+4、100℃〕)。 <Mooney viscosity (Compound Mooney)>
The Mooney viscosity (compound Mooney) of the crosslinkable nitrile rubber composition was measured according to JIS K6300-1 (unit: [ML1 + 4, 100 ° C.]).
<架橋速度>
架橋性ニトリルゴム組成物について、ゴム架橋試験機(RPA2000、アルファテクノロジーズ社製)を用い、160℃、30分の条件で架橋性試験を行った。そして、架橋性試験の結果から、T10(単位は、min.)を測定した。なお、T10は、「最大トルクMH-最小トルクML」を100%としたときに、トルクが最小トルクMLから、10%上昇するのに要する時間を意味し、T10の値が大きいほど、架橋速度が緩慢であり、架橋安定性に優れると判断できる。 <Crosslinking speed>
The crosslinkability test was performed on the crosslinkable nitrile rubber composition using a rubber crosslinking tester (RPA2000, manufactured by Alpha Technologies) at 160 ° C. for 30 minutes. Then, T 10 (unit: min.) Was measured from the result of the crosslinking property test. Incidentally, T 10 is the "maximum torque MH- minimum torque ML" is taken as 100%, the torque from the minimum torque ML, means the time required for 10% increase, as the value of T 10 is large, It can be judged that the crosslinking speed is slow and the crosslinking stability is excellent.
架橋性ニトリルゴム組成物について、ゴム架橋試験機(RPA2000、アルファテクノロジーズ社製)を用い、160℃、30分の条件で架橋性試験を行った。そして、架橋性試験の結果から、T10(単位は、min.)を測定した。なお、T10は、「最大トルクMH-最小トルクML」を100%としたときに、トルクが最小トルクMLから、10%上昇するのに要する時間を意味し、T10の値が大きいほど、架橋速度が緩慢であり、架橋安定性に優れると判断できる。 <Crosslinking speed>
The crosslinkability test was performed on the crosslinkable nitrile rubber composition using a rubber crosslinking tester (RPA2000, manufactured by Alpha Technologies) at 160 ° C. for 30 minutes. Then, T 10 (unit: min.) Was measured from the result of the crosslinking property test. Incidentally, T 10 is the "maximum torque MH- minimum torque ML" is taken as 100%, the torque from the minimum torque ML, means the time required for 10% increase, as the value of T 10 is large, It can be judged that the crosslinking speed is slow and the crosslinking stability is excellent.
<常態物性(引張強度、伸び、硬さ)>
架橋性ニトリルゴム組成物を、縦15cm、横15cm、深さ0.2cmの金型に入れ、プレス圧10MPaで加圧しながら160℃で20分間プレス成形してシート状のゴム架橋物を得た。得られたシート状のゴム架橋物をJIS3号形ダンベルで打ち抜いて試験片を作製した。そして、得られた試験片を用いて、JIS K6251に従い、ゴム架橋物の引張強度、および破断時の伸びを、また、JIS K6253-3:2012に従い、デュロメータ硬さ試験機(タイプA)を用いてゴム架橋物の硬さを、それぞれ測定した。 <Normal physical properties (tensile strength, elongation, hardness)>
The crosslinkable nitrile rubber composition was placed in a mold having a length of 15 cm, a width of 15 cm, and a depth of 0.2 cm, and press-molded at 160 ° C. for 20 minutes while applying a pressure of 10 MPa to obtain a sheet-like rubber cross-linked product. . A test piece was prepared by punching out the obtained sheet cross-linked rubber with a JIS No. 3 dumbbell. Then, using the obtained test piece, the tensile strength and elongation at break of the rubber crosslinked product were measured according to JIS K6251, and a durometer hardness tester (type A) was used according to JIS K6253-3: 2012. The hardness of the rubber crosslinked product was measured in each case.
架橋性ニトリルゴム組成物を、縦15cm、横15cm、深さ0.2cmの金型に入れ、プレス圧10MPaで加圧しながら160℃で20分間プレス成形してシート状のゴム架橋物を得た。得られたシート状のゴム架橋物をJIS3号形ダンベルで打ち抜いて試験片を作製した。そして、得られた試験片を用いて、JIS K6251に従い、ゴム架橋物の引張強度、および破断時の伸びを、また、JIS K6253-3:2012に従い、デュロメータ硬さ試験機(タイプA)を用いてゴム架橋物の硬さを、それぞれ測定した。 <Normal physical properties (tensile strength, elongation, hardness)>
The crosslinkable nitrile rubber composition was placed in a mold having a length of 15 cm, a width of 15 cm, and a depth of 0.2 cm, and press-molded at 160 ° C. for 20 minutes while applying a pressure of 10 MPa to obtain a sheet-like rubber cross-linked product. . A test piece was prepared by punching out the obtained sheet cross-linked rubber with a JIS No. 3 dumbbell. Then, using the obtained test piece, the tensile strength and elongation at break of the rubber crosslinked product were measured according to JIS K6251, and a durometer hardness tester (type A) was used according to JIS K6253-3: 2012. The hardness of the rubber crosslinked product was measured in each case.
<圧縮永久歪み試験>
架橋性ニトリルゴム組成物を、金型を用いて、加圧しながら温度160℃で30分間プレスすることにより、直径29mm、高さ12.5mmの円柱型のゴム架橋物を得た。そして、得られたゴム架橋物を用いて、JIS K6262に従い、ゴム架橋物を25%圧縮させた状態で、100℃の環境下に70時間置いた後、圧縮永久歪みを測定した。この値が小さいほど、耐圧縮永久歪み性に優れる。 <Compression set test>
The crosslinkable nitrile rubber composition was pressed using a mold at a temperature of 160 ° C. for 30 minutes while applying pressure, thereby obtaining a columnar rubber crosslinked product having a diameter of 29 mm and a height of 12.5 mm. Using the obtained rubber crosslinked product, the rubber crosslinked product was placed in an environment of 100 ° C. for 70 hours in a state of being compressed by 25% in accordance with JIS K6262, and then the compression set was measured. The smaller the value, the more excellent the compression set resistance.
架橋性ニトリルゴム組成物を、金型を用いて、加圧しながら温度160℃で30分間プレスすることにより、直径29mm、高さ12.5mmの円柱型のゴム架橋物を得た。そして、得られたゴム架橋物を用いて、JIS K6262に従い、ゴム架橋物を25%圧縮させた状態で、100℃の環境下に70時間置いた後、圧縮永久歪みを測定した。この値が小さいほど、耐圧縮永久歪み性に優れる。 <Compression set test>
The crosslinkable nitrile rubber composition was pressed using a mold at a temperature of 160 ° C. for 30 minutes while applying pressure, thereby obtaining a columnar rubber crosslinked product having a diameter of 29 mm and a height of 12.5 mm. Using the obtained rubber crosslinked product, the rubber crosslinked product was placed in an environment of 100 ° C. for 70 hours in a state of being compressed by 25% in accordance with JIS K6262, and then the compression set was measured. The smaller the value, the more excellent the compression set resistance.
<圧縮応力緩和試験>
架橋性ニトリルゴム組成物を、金型を用いて、加圧しながら温度160℃で30分間プレスすることにより、直径29mm、高さ12.5mmの円柱型のゴム架橋物を得た。そして、得られたゴム架橋物を25%圧縮させた状態で、125℃の環境下に保持することで、圧縮応力緩和試験を行った。そして、試験開始から30分後に、ゴム架橋物の圧縮応力を測定し、これを初期応力とし、試験開始後72時間後の圧縮応力を測定し、下記式にしたがって、圧縮応力保持率を求めた。
圧縮応力保持率[%]=(72時間後の圧縮応力[MPa]/初期応力[MPa])×100
本実施例においては、上記式に従って求めた圧縮応力保持率が30%以上であった場合には「〇」と評価し、上記式に従って求めた圧縮応力保持率が30%未満であった場合には「×」と評価した。 <Compression stress relaxation test>
The crosslinkable nitrile rubber composition was pressed using a mold at a temperature of 160 ° C. for 30 minutes while applying pressure, thereby obtaining a columnar rubber crosslinked product having a diameter of 29 mm and a height of 12.5 mm. Then, a compression stress relaxation test was performed by maintaining the obtained crosslinked rubber in an environment of 125 ° C. in a state of being compressed by 25%. Then, 30 minutes after the start of the test, the compressive stress of the rubber crosslinked product was measured, and this was taken as the initial stress. The compressive stress 72 hours after the start of the test was measured, and the compressive stress retention was determined according to the following equation. .
Compressive stress retention [%] = (Compressive stress [MPa] after 72 hours / Initial stress [MPa]) × 100
In this example, when the compressive stress retention obtained according to the above equation was 30% or more, it was evaluated as “Δ”. When the compressive stress retention obtained according to the above equation was less than 30%, Was evaluated as "x".
架橋性ニトリルゴム組成物を、金型を用いて、加圧しながら温度160℃で30分間プレスすることにより、直径29mm、高さ12.5mmの円柱型のゴム架橋物を得た。そして、得られたゴム架橋物を25%圧縮させた状態で、125℃の環境下に保持することで、圧縮応力緩和試験を行った。そして、試験開始から30分後に、ゴム架橋物の圧縮応力を測定し、これを初期応力とし、試験開始後72時間後の圧縮応力を測定し、下記式にしたがって、圧縮応力保持率を求めた。
圧縮応力保持率[%]=(72時間後の圧縮応力[MPa]/初期応力[MPa])×100
本実施例においては、上記式に従って求めた圧縮応力保持率が30%以上であった場合には「〇」と評価し、上記式に従って求めた圧縮応力保持率が30%未満であった場合には「×」と評価した。 <Compression stress relaxation test>
The crosslinkable nitrile rubber composition was pressed using a mold at a temperature of 160 ° C. for 30 minutes while applying pressure, thereby obtaining a columnar rubber crosslinked product having a diameter of 29 mm and a height of 12.5 mm. Then, a compression stress relaxation test was performed by maintaining the obtained crosslinked rubber in an environment of 125 ° C. in a state of being compressed by 25%. Then, 30 minutes after the start of the test, the compressive stress of the rubber crosslinked product was measured, and this was taken as the initial stress. The compressive stress 72 hours after the start of the test was measured, and the compressive stress retention was determined according to the following equation. .
Compressive stress retention [%] = (Compressive stress [MPa] after 72 hours / Initial stress [MPa]) × 100
In this example, when the compressive stress retention obtained according to the above equation was 30% or more, it was evaluated as “Δ”. When the compressive stress retention obtained according to the above equation was less than 30%, Was evaluated as "x".
<ゲーマン捻り試験(耐寒性)>
上記常態物性の評価と同様にして、シート状のゴム架橋物を得た後、得られたシート状のゴム架橋物について、JIS K6261-3:2017に準拠して、ゲーマン捻り試験を行い、室温(23℃)のモジュラスに対する比モジュラスが10倍になる温度T10を測定した。T10の値が低いほど耐寒性に優れると判断できる。 <Geman twist test (cold resistance)>
After obtaining a sheet-like rubber crosslinked product in the same manner as in the evaluation of the normal physical properties, the obtained sheet-like rubber crosslinked product was subjected to a Gehman torsion test in accordance with JIS K6261-3: 2017. The temperature T10 at which the specific modulus with respect to the modulus of (23 ° C.) became 10 times was measured. It can be determined that the lower the value of T10, the better the cold resistance.
上記常態物性の評価と同様にして、シート状のゴム架橋物を得た後、得られたシート状のゴム架橋物について、JIS K6261-3:2017に準拠して、ゲーマン捻り試験を行い、室温(23℃)のモジュラスに対する比モジュラスが10倍になる温度T10を測定した。T10の値が低いほど耐寒性に優れると判断できる。 <Geman twist test (cold resistance)>
After obtaining a sheet-like rubber crosslinked product in the same manner as in the evaluation of the normal physical properties, the obtained sheet-like rubber crosslinked product was subjected to a Gehman torsion test in accordance with JIS K6261-3: 2017. The temperature T10 at which the specific modulus with respect to the modulus of (23 ° C.) became 10 times was measured. It can be determined that the lower the value of T10, the better the cold resistance.
<実施例1>
(第1の混合工程)
バンバリーミキサを用いて、水素化アクリロニトリル-ブタジエンゴム(A-1)(商品名「Zetpol 0020」、アクリロニトリル単量体単位49重量%、ヨウ素価23)30部、水素化アクリロニトリル-ブタジエンゴム(A-2)(商品名「Zetpol 1020」、アクリロニトリル単量体単位44重量%、ヨウ素価24)30部、塩化ビニル樹脂(商品名「TK1300」、信越化学工業社製、平均重合度1300)40部、カルシウム-マグネシウム-亜鉛系安定剤(商品名「アデカスタブRUP-110」、ADEKA社製)0.5部、および、ポリエーテルエステル(c1-1)(商品名「アデカサイザー RS-700」、ADEKA社製、分子量:550、25℃における粘度:30mPa・s、引火点:221℃、上記一般式(1)で表されるポリエーテルエステル(c1))10部を投入し、50℃で5分間混練し、さらにロールにて175℃で5分混合することにより、第1の混合工程による組成物を得た。なお、水素化アクリロニトリル-ブタジエンゴム(A-1)と、水素化アクリロニトリル-ブタジエンゴム(A-2)との混合物は、混合物としてのアクリロニトリル単量体単位量が46.5重量%、ヨウ素価が23.5であった。 <Example 1>
(First mixing step)
Using a Banbury mixer, 30 parts of hydrogenated acrylonitrile-butadiene rubber (A-1) (trade name “Zetpol 0020”, acrylonitrile monomer unit 49% by weight, iodine value 23), hydrogenated acrylonitrile-butadiene rubber (A- 2) 30 parts of (trade name "Zetpol 1020", acrylonitrile monomer unit 44% by weight, iodine value 24) 30 parts, vinyl chloride resin (trade name "TK1300", Shin-Etsu Chemical Co., Ltd., average polymerization degree 1300) 40 parts, 0.5 parts of a calcium-magnesium-zinc-based stabilizer (trade name “ADEKA STAB RUP-110”, manufactured by ADEKA) and polyetherester (c1-1) (trade name “ADEKA SIZER RS-700”, manufactured by ADEKA) Molecular weight: 550, viscosity at 25 ° C .: 30 mPa · s, flash point: 221 ° C. 10 parts of the polyetherester (c1) represented by the above general formula (1) is charged, kneaded at 50 ° C. for 5 minutes, and further mixed at 175 ° C. for 5 minutes with a roll to form a first mixing step. Was obtained. The mixture of the hydrogenated acrylonitrile-butadiene rubber (A-1) and the hydrogenated acrylonitrile-butadiene rubber (A-2) has an acrylonitrile monomer unit amount of 46.5% by weight and an iodine value of the mixture. 23.5.
(第1の混合工程)
バンバリーミキサを用いて、水素化アクリロニトリル-ブタジエンゴム(A-1)(商品名「Zetpol 0020」、アクリロニトリル単量体単位49重量%、ヨウ素価23)30部、水素化アクリロニトリル-ブタジエンゴム(A-2)(商品名「Zetpol 1020」、アクリロニトリル単量体単位44重量%、ヨウ素価24)30部、塩化ビニル樹脂(商品名「TK1300」、信越化学工業社製、平均重合度1300)40部、カルシウム-マグネシウム-亜鉛系安定剤(商品名「アデカスタブRUP-110」、ADEKA社製)0.5部、および、ポリエーテルエステル(c1-1)(商品名「アデカサイザー RS-700」、ADEKA社製、分子量:550、25℃における粘度:30mPa・s、引火点:221℃、上記一般式(1)で表されるポリエーテルエステル(c1))10部を投入し、50℃で5分間混練し、さらにロールにて175℃で5分混合することにより、第1の混合工程による組成物を得た。なお、水素化アクリロニトリル-ブタジエンゴム(A-1)と、水素化アクリロニトリル-ブタジエンゴム(A-2)との混合物は、混合物としてのアクリロニトリル単量体単位量が46.5重量%、ヨウ素価が23.5であった。 <Example 1>
(First mixing step)
Using a Banbury mixer, 30 parts of hydrogenated acrylonitrile-butadiene rubber (A-1) (trade name “Zetpol 0020”, acrylonitrile monomer unit 49% by weight, iodine value 23), hydrogenated acrylonitrile-butadiene rubber (A- 2) 30 parts of (trade name "Zetpol 1020", acrylonitrile monomer unit 44% by weight, iodine value 24) 30 parts, vinyl chloride resin (trade name "TK1300", Shin-Etsu Chemical Co., Ltd., average polymerization degree 1300) 40 parts, 0.5 parts of a calcium-magnesium-zinc-based stabilizer (trade name “ADEKA STAB RUP-110”, manufactured by ADEKA) and polyetherester (c1-1) (trade name “ADEKA SIZER RS-700”, manufactured by ADEKA) Molecular weight: 550, viscosity at 25 ° C .: 30 mPa · s, flash point: 221 ° C. 10 parts of the polyetherester (c1) represented by the above general formula (1) is charged, kneaded at 50 ° C. for 5 minutes, and further mixed at 175 ° C. for 5 minutes with a roll to form a first mixing step. Was obtained. The mixture of the hydrogenated acrylonitrile-butadiene rubber (A-1) and the hydrogenated acrylonitrile-butadiene rubber (A-2) has an acrylonitrile monomer unit amount of 46.5% by weight and an iodine value of the mixture. 23.5.
(第2の混合工程)
次いで、バンバリーミキサを用いて、上記にて得られた第1の混合工程による組成物の全量110.5部、カーボンブラック(商品名「シーストS」、東海カーボン社製)30部、ポリエーテルエステル(c1-1)(商品名「アデカサイザー RS-700」、ADEKA社製)5部、4,4’-ジ-(α,α-ジメチルベンジル)ジフェニルアミン(商品名「ノクラック CD」、大内新興化学工業社製、老化防止剤)1.5部、2-メルカプトベンゾイミダゾール(法品名「ノクラックMB」、大内新興化学工業社製、老化防止剤)1部、ステアリン酸1部、酸化亜鉛(商品名「酸化亜鉛2種」、正同化学工業社製)5部、N-イソプロピル-N’-フェニル-p-フェニレンジアミン(商品名「ノクラック810NA」、大内新興化学工業社製、老化防止剤)1.5部、2,2,4-トリメチル-1,2-ジハイドロキノリン(商品名「ノクラック224」、大内新興化学工業社製、老化防止剤)1.5部、およびワックス(商品名「サンタイトS」、精工化学社製)0.5部を配合して、50℃で5分間混練した。次いで、得られた混合物を50℃のロールに移して、4,4’-ジチオジモルホリン(商品名「バルノックR」、大内新興化学工業社製、架橋剤)2部、テトラメチルチウラムジスルフィド(商品名「ノクセラーTT」、大内新興化学工業社製、架橋促進剤)1.5部、およびN-シクロヘキシル-2-ベンゾチアゾリルスルフェンアミド(商品名「ノクセラーCZ」、大内新興化学工業社製、架橋促進剤)1.5部を配合して、混練することにより、架橋性ニトリルゴム組成物を得た。 (Second mixing step)
Next, using a Banbury mixer, 110.5 parts of the total amount of the composition obtained in the first mixing step obtained above, 30 parts of carbon black (trade name “SEIST S”, manufactured by Tokai Carbon Co., Ltd.), polyetherester (C1-1) 5 parts (trade name “ADEKASIZER RS-700”, manufactured by ADEKA), 4,4′-di- (α, α-dimethylbenzyl) diphenylamine (trade name “Nocrack CD”, Ouchi Shinko) 1.5 parts of 2-mercaptobenzimidazole (product name "Nocrack MB", Ouchi Shinko Chemical Co., Ltd., anti-aging agent), 1.5 parts of stearic acid, 1 part of stearic acid, zinc oxide (manufactured by Chemical Industry Co., Ltd.) Trade name “2 kinds of zinc oxide”, 5 parts by Shodo Chemical Co., Ltd., N-isopropyl-N′-phenyl-p-phenylenediamine (trade name “Nocrack 810NA”, Ouchi Shinko Chemical Industry Co., Ltd.) 1.5 parts of 2,2,4-trimethyl-1,2-dihydroquinoline (trade name "Nocrack 224", manufactured by Ouchi Shinko Chemical Co., Ltd., 1.5 parts) And 0.5 parts of wax (trade name “Suntight S”, manufactured by Seiko Chemical Co., Ltd.) were mixed and kneaded at 50 ° C. for 5 minutes. Next, the obtained mixture was transferred to a roll at 50 ° C., and 2 parts of 4,4′-dithiodimorpholine (trade name “Barnock R”, manufactured by Ouchi Shinko Chemical Co., Ltd., a crosslinking agent), and tetramethylthiuram disulfide (2 parts) Brand name “Noxeller TT”, 1.5 parts of Ouchi Shinko Chemical Co., Ltd., crosslinking accelerator), and N-cyclohexyl-2-benzothiazolylsulfenamide (brand name “Noxeller CZ”, Ouchi Shinko Chemical Industry) (Cross-linking accelerator), 1.5 parts, and kneaded to obtain a cross-linkable nitrile rubber composition.
次いで、バンバリーミキサを用いて、上記にて得られた第1の混合工程による組成物の全量110.5部、カーボンブラック(商品名「シーストS」、東海カーボン社製)30部、ポリエーテルエステル(c1-1)(商品名「アデカサイザー RS-700」、ADEKA社製)5部、4,4’-ジ-(α,α-ジメチルベンジル)ジフェニルアミン(商品名「ノクラック CD」、大内新興化学工業社製、老化防止剤)1.5部、2-メルカプトベンゾイミダゾール(法品名「ノクラックMB」、大内新興化学工業社製、老化防止剤)1部、ステアリン酸1部、酸化亜鉛(商品名「酸化亜鉛2種」、正同化学工業社製)5部、N-イソプロピル-N’-フェニル-p-フェニレンジアミン(商品名「ノクラック810NA」、大内新興化学工業社製、老化防止剤)1.5部、2,2,4-トリメチル-1,2-ジハイドロキノリン(商品名「ノクラック224」、大内新興化学工業社製、老化防止剤)1.5部、およびワックス(商品名「サンタイトS」、精工化学社製)0.5部を配合して、50℃で5分間混練した。次いで、得られた混合物を50℃のロールに移して、4,4’-ジチオジモルホリン(商品名「バルノックR」、大内新興化学工業社製、架橋剤)2部、テトラメチルチウラムジスルフィド(商品名「ノクセラーTT」、大内新興化学工業社製、架橋促進剤)1.5部、およびN-シクロヘキシル-2-ベンゾチアゾリルスルフェンアミド(商品名「ノクセラーCZ」、大内新興化学工業社製、架橋促進剤)1.5部を配合して、混練することにより、架橋性ニトリルゴム組成物を得た。 (Second mixing step)
Next, using a Banbury mixer, 110.5 parts of the total amount of the composition obtained in the first mixing step obtained above, 30 parts of carbon black (trade name “SEIST S”, manufactured by Tokai Carbon Co., Ltd.), polyetherester (C1-1) 5 parts (trade name “ADEKASIZER RS-700”, manufactured by ADEKA), 4,4′-di- (α, α-dimethylbenzyl) diphenylamine (trade name “Nocrack CD”, Ouchi Shinko) 1.5 parts of 2-mercaptobenzimidazole (product name "Nocrack MB", Ouchi Shinko Chemical Co., Ltd., anti-aging agent), 1.5 parts of stearic acid, 1 part of stearic acid, zinc oxide (manufactured by Chemical Industry Co., Ltd.) Trade name “2 kinds of zinc oxide”, 5 parts by Shodo Chemical Co., Ltd., N-isopropyl-N′-phenyl-p-phenylenediamine (trade name “Nocrack 810NA”, Ouchi Shinko Chemical Industry Co., Ltd.) 1.5 parts of 2,2,4-trimethyl-1,2-dihydroquinoline (trade name "Nocrack 224", manufactured by Ouchi Shinko Chemical Co., Ltd., 1.5 parts) And 0.5 parts of wax (trade name “Suntight S”, manufactured by Seiko Chemical Co., Ltd.) were mixed and kneaded at 50 ° C. for 5 minutes. Next, the obtained mixture was transferred to a roll at 50 ° C., and 2 parts of 4,4′-dithiodimorpholine (trade name “Barnock R”, manufactured by Ouchi Shinko Chemical Co., Ltd., a crosslinking agent), and tetramethylthiuram disulfide (2 parts) Brand name “Noxeller TT”, 1.5 parts of Ouchi Shinko Chemical Co., Ltd., crosslinking accelerator), and N-cyclohexyl-2-benzothiazolylsulfenamide (brand name “Noxeller CZ”, Ouchi Shinko Chemical Industry) (Cross-linking accelerator), 1.5 parts, and kneaded to obtain a cross-linkable nitrile rubber composition.
そして、得られた架橋性ニトリルゴム組成物を用いて、ムーニー粘度(コンパウンド・ムーニー)、架橋速度、および常態物性(引張強度、伸び、硬さ)の測定、ならびに、圧縮永久歪み試験、圧縮応力緩和試験、およびゲーマン捻り試験の各試験を行った。結果を表1に示す。
Then, using the obtained crosslinkable nitrile rubber composition, measurement of Mooney viscosity (compound Mooney), crosslinking speed, and physical properties in normal state (tensile strength, elongation, hardness), compression set test, compression stress Each test of the relaxation test and the Gehman torsion test was performed. Table 1 shows the results.
<実施例2>
第1混合工程および第2混合工程において、可塑剤として、ポリエーテルエステル(c1-1)(商品名「アデカサイザー RS-700」、ADEKA社製)に代えて、いずれも、ポリエーテルエステル(c1-2)(商品名「アデカサイザー RS-735」、ADEKA社製、分子量:850、25℃における粘度:80mPa・s、引火点:252℃、上記一般式(1)で表されるポリエーテルエステル(c1))を同じ量使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表1に示す。 <Example 2>
In the first mixing step and the second mixing step, the plasticizer was replaced with polyetherester (c1-1) (trade name “ADEKASIZER RS-700”, manufactured by ADEKA), and both were mixed with polyetherester (c1). -2) (trade name "ADEKA SIZER RS-735", manufactured by ADEKA Corporation, molecular weight: 850, viscosity at 25 ° C: 80 mPa · s, flash point: 252 ° C, polyether ester represented by the above general formula (1)) A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner as in Example 1 except that the same amount of (c1)) was used. Table 1 shows the results.
第1混合工程および第2混合工程において、可塑剤として、ポリエーテルエステル(c1-1)(商品名「アデカサイザー RS-700」、ADEKA社製)に代えて、いずれも、ポリエーテルエステル(c1-2)(商品名「アデカサイザー RS-735」、ADEKA社製、分子量:850、25℃における粘度:80mPa・s、引火点:252℃、上記一般式(1)で表されるポリエーテルエステル(c1))を同じ量使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表1に示す。 <Example 2>
In the first mixing step and the second mixing step, the plasticizer was replaced with polyetherester (c1-1) (trade name “ADEKASIZER RS-700”, manufactured by ADEKA), and both were mixed with polyetherester (c1). -2) (trade name "ADEKA SIZER RS-735", manufactured by ADEKA Corporation, molecular weight: 850, viscosity at 25 ° C: 80 mPa · s, flash point: 252 ° C, polyether ester represented by the above general formula (1)) A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner as in Example 1 except that the same amount of (c1)) was used. Table 1 shows the results.
<実施例3>
第1混合工程および第2混合工程において、可塑剤として、ポリエーテルエステル(c1-1)(商品名「アデカサイザー RS-700」、ADEKA社製)に代えて、いずれも、アジピン酸系ポリエステル(c2-1)(商品名「アデカサイザー PN-170」、ADEKA社製、分子量:1100、25℃における粘度:800mPa・s、引火点:244℃、アジピン酸系ポリエステル(c2))を同じ量使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表1に示す。 <Example 3>
In the first mixing step and the second mixing step, as the plasticizer, in place of the polyetherester (c1-1) (trade name “ADEKASIZER RS-700”, manufactured by ADEKA Corporation), any of adipic acid-based polyester ( c2-1) (trade name “ADEKASIZER PN-170”, manufactured by ADEKA Corporation, molecular weight: 1100, viscosity at 25 ° C .: 800 mPa · s, flash point: 244 ° C., adipic acid-based polyester (c2)) used in the same amount A crosslinkable nitrile rubber composition was obtained in the same manner as in Example 1 except that the evaluation was performed, and the evaluation was performed in the same manner. Table 1 shows the results.
第1混合工程および第2混合工程において、可塑剤として、ポリエーテルエステル(c1-1)(商品名「アデカサイザー RS-700」、ADEKA社製)に代えて、いずれも、アジピン酸系ポリエステル(c2-1)(商品名「アデカサイザー PN-170」、ADEKA社製、分子量:1100、25℃における粘度:800mPa・s、引火点:244℃、アジピン酸系ポリエステル(c2))を同じ量使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表1に示す。 <Example 3>
In the first mixing step and the second mixing step, as the plasticizer, in place of the polyetherester (c1-1) (trade name “ADEKASIZER RS-700”, manufactured by ADEKA Corporation), any of adipic acid-based polyester ( c2-1) (trade name “ADEKASIZER PN-170”, manufactured by ADEKA Corporation, molecular weight: 1100, viscosity at 25 ° C .: 800 mPa · s, flash point: 244 ° C., adipic acid-based polyester (c2)) used in the same amount A crosslinkable nitrile rubber composition was obtained in the same manner as in Example 1 except that the evaluation was performed, and the evaluation was performed in the same manner. Table 1 shows the results.
<実施例4>
第2混合工程において、酸化亜鉛5部に代えて、カルシウム-マグネシウム-亜鉛系安定剤(商品名「アデカスタブRUP-110」、ADEKA社製)を15部使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表1に示す。 <Example 4>
In the second mixing step, the same procedure as in Example 1 was carried out, except that 15 parts of a calcium-magnesium-zinc-based stabilizer (trade name “ADK STAB RUP-110”, manufactured by ADEKA) was used instead of 5 parts of zinc oxide. Thus, a crosslinkable nitrile rubber composition was obtained and similarly evaluated. Table 1 shows the results.
第2混合工程において、酸化亜鉛5部に代えて、カルシウム-マグネシウム-亜鉛系安定剤(商品名「アデカスタブRUP-110」、ADEKA社製)を15部使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表1に示す。 <Example 4>
In the second mixing step, the same procedure as in Example 1 was carried out, except that 15 parts of a calcium-magnesium-zinc-based stabilizer (trade name “ADK STAB RUP-110”, manufactured by ADEKA) was used instead of 5 parts of zinc oxide. Thus, a crosslinkable nitrile rubber composition was obtained and similarly evaluated. Table 1 shows the results.
<比較例1>
第1混合工程および第2混合工程において、可塑剤として、ポリエーテルエステル(c1-1)(商品名「アデカサイザー RS-700」、ADEKA社製)に代えて、いずれも、アジピン酸ポリエーテルエステル(商品名「アデカサイザー RS-107」、ADEKA社製、分子量:434、25℃における粘度:20mPa・s、引火点:215℃、)を同じ量使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表1に示す。 <Comparative Example 1>
In the first mixing step and the second mixing step, as the plasticizer, adipic acid polyether ester was used instead of polyether ester (c1-1) (trade name “ADEKASIZER RS-700” manufactured by ADEKA). (Product name “ADEKASIZER RS-107”, manufactured by ADEKA Corporation, molecular weight: 434, viscosity at 25 ° C .: 20 mPa · s, flash point: 215 ° C.), except that the same amount was used. A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner. Table 1 shows the results.
第1混合工程および第2混合工程において、可塑剤として、ポリエーテルエステル(c1-1)(商品名「アデカサイザー RS-700」、ADEKA社製)に代えて、いずれも、アジピン酸ポリエーテルエステル(商品名「アデカサイザー RS-107」、ADEKA社製、分子量:434、25℃における粘度:20mPa・s、引火点:215℃、)を同じ量使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表1に示す。 <Comparative Example 1>
In the first mixing step and the second mixing step, as the plasticizer, adipic acid polyether ester was used instead of polyether ester (c1-1) (trade name “ADEKASIZER RS-700” manufactured by ADEKA). (Product name “ADEKASIZER RS-107”, manufactured by ADEKA Corporation, molecular weight: 434, viscosity at 25 ° C .: 20 mPa · s, flash point: 215 ° C.), except that the same amount was used. A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner. Table 1 shows the results.
<比較例2>
第2混合工程において、架橋剤として、4,4’-ジチオジモルホリン2部に代えて、硫黄0.5部を使用した以外は、比較例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表1に示す。 <Comparative Example 2>
In the second mixing step, a crosslinkable nitrile rubber composition was prepared in the same manner as in Comparative Example 1 except that 0.5 parts of sulfur was used instead of 2 parts of 4,4′-dithiodimorpholine as a crosslinker. Obtained and evaluated similarly. Table 1 shows the results.
第2混合工程において、架橋剤として、4,4’-ジチオジモルホリン2部に代えて、硫黄0.5部を使用した以外は、比較例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表1に示す。 <Comparative Example 2>
In the second mixing step, a crosslinkable nitrile rubber composition was prepared in the same manner as in Comparative Example 1 except that 0.5 parts of sulfur was used instead of 2 parts of 4,4′-dithiodimorpholine as a crosslinker. Obtained and evaluated similarly. Table 1 shows the results.
表1に示すように、α,β-エチレン性不飽和ニトリル単量体単位を40~50重量%の割合で含有し、ヨウ素価が5~50であるニトリル基含有共重合体ゴム(A)と、塩化ビニル樹脂(B)と、分子量が500~2000である可塑剤(C)と、を含有するニトリルゴム組成物(架橋性ニトリルゴム組成物)によれば、コンパウンド・ムーニー粘度の上昇が抑えられており、加工性に優れ、粘度が10%上昇する時間T10が長く、架橋安定性に優れ、得られるゴム架橋物は、常態物性が良好であり、圧縮永久歪みが小さく、圧縮応力保持率が高く、耐寒性に優れるものであった(実施例1~4)。
As shown in Table 1, a nitrile group-containing copolymer rubber (A) containing α, β-ethylenically unsaturated nitrile monomer units at a ratio of 40 to 50% by weight and an iodine value of 5 to 50 According to the nitrile rubber composition (crosslinkable nitrile rubber composition) containing the vinyl chloride resin (B) and the plasticizer (C) having a molecular weight of 500 to 2,000, the compound Mooney viscosity increases. It suppressed to have excellent processability, long time T 10 that viscosity increases 10%, excellent in crosslinking stability, the obtained rubber cross-linked product, a normal physical properties good, compression set is small, compressive stress It had a high retention and excellent cold resistance (Examples 1 to 4).
一方、分子量が500~2000である可塑剤(C)に代えて、分子量が500未満であるアジピン酸ポリエーテルエステル系可塑剤を使用した場合には、得られるゴム架橋物は、圧縮永久歪が大きく、圧縮応力保持率に劣るものであった(比較例1,2)。
On the other hand, when a plasticizer of adipic acid polyether ester having a molecular weight of less than 500 is used instead of the plasticizer (C) having a molecular weight of 500 to 2,000, the obtained rubber cross-linked product has a compression set. It was large and inferior in compressive stress retention (Comparative Examples 1 and 2).
Claims (9)
- α,β-エチレン性不飽和ニトリル単量体単位を40~50重量%の割合で含有し、ヨウ素価が5~50であるニトリル基含有共重合体ゴム(A)と、
塩化ビニル樹脂(B)と、
分子量が500~2000である可塑剤(C)と、を含有するニトリルゴム組成物。 a nitrile group-containing copolymer rubber (A) containing 40 to 50% by weight of α, β-ethylenically unsaturated nitrile monomer units and having an iodine value of 5 to 50;
A vinyl chloride resin (B),
A nitrile rubber composition comprising a plasticizer (C) having a molecular weight of 500 to 2,000. - 前記可塑剤(C)が、下記一般式(1)で表されるポリエーテルエステル(c1)である請求項1に記載のニトリルゴム組成物。
- 前記可塑剤(C)が、分子量が800~2000であり、温度25℃における粘度が50~1500mPa・sであるアジピン酸系ポリエステル(c2)である請求項1に記載のニトリルゴム組成物。 ニ The nitrile rubber composition according to claim 1, wherein the plasticizer (C) is an adipic acid-based polyester (c2) having a molecular weight of 800 to 2,000 and a viscosity at a temperature of 25 ° C of 50 to 1500 mPa · s.
- 前記ニトリル基含有共重合体ゴム(A)100重量部に対する、前記可塑剤(C)の含有量が1~60重量部である請求項1~3のいずれかに記載のニトリルゴム組成物。 4. The nitrile rubber composition according to claim 1, wherein the content of the plasticizer (C) is 1 to 60 parts by weight based on 100 parts by weight of the nitrile group-containing copolymer rubber (A).
- 請求項1~4のいずれかに記載のニトリルゴム組成物と、架橋剤とを含有する架橋性ニトリルゴム組成物。 A crosslinkable nitrile rubber composition comprising the nitrile rubber composition according to any one of claims 1 to 4 and a crosslinking agent.
- 請求項5に記載の架橋性ニトリルゴム組成物を架橋してなるゴム架橋物。 A rubber crosslinked product obtained by crosslinking the crosslinkable nitrile rubber composition according to claim 5.
- α,β-エチレン性不飽和ニトリル単量体単位を40~50重量%の割合で含有し、ヨウ素価が5~50であるニトリル基含有共重合体ゴム(A)と、塩化ビニル樹脂(B)と、分子量が500~2000である可塑剤(C)と、配合剤とを含有するニトリルゴム組成物を製造する方法であって、
前記ニトリルゴム組成物中に含有させる前記可塑剤(C)の全量のうち一部を、前記ニトリル基含有共重合体ゴム(A)と、前記塩化ビニル樹脂(B)と混合する第1の混合工程と、
前記第1の混合工程において得られた組成物に、前記ニトリルゴム組成物に含有させる前記可塑剤(C)の全量のうち残部と、前記配合剤とを配合し、混合する第2混合工程とを備えるニトリルゴム組成物の製造方法。 a nitrile group-containing copolymer rubber (A) containing an α, β-ethylenically unsaturated nitrile monomer unit at a ratio of 40 to 50% by weight and an iodine value of 5 to 50, and a vinyl chloride resin (B ), A plasticizer (C) having a molecular weight of 500 to 2,000, and a compounding agent, the method comprising the steps of:
First mixing in which a part of the total amount of the plasticizer (C) to be contained in the nitrile rubber composition is mixed with the nitrile group-containing copolymer rubber (A) and the vinyl chloride resin (B). Process and
A second mixing step in which the composition obtained in the first mixing step is mixed with the rest of the total amount of the plasticizer (C) to be contained in the nitrile rubber composition and the compounding agent, and a second mixing step is performed. A method for producing a nitrile rubber composition comprising: - 前記第1混合工程における前記可塑剤(C)の配合量を、前記ニトリルゴム組成物中に含有させる前記可塑剤(C)の全量のうち、10~90重量%とする請求項7に記載のニトリルゴム組成物の製造方法。 8. The method according to claim 7, wherein the amount of the plasticizer (C) in the first mixing step is 10 to 90% by weight based on the total amount of the plasticizer (C) contained in the nitrile rubber composition. A method for producing a nitrile rubber composition.
- 前記配合剤が、少なくとも充填剤を含む請求項7または8に記載のニトリルゴム組成物の製造方法。 方法 The method for producing a nitrile rubber composition according to claim 7 or 8, wherein the compounding agent contains at least a filler.
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59100152A (en) * | 1982-11-30 | 1984-06-09 | Toyoda Gosei Co Ltd | Vinyl chloride resin composition |
JPH06263924A (en) * | 1993-03-16 | 1994-09-20 | Nippon Zeon Co Ltd | Rubber composition |
JPH07292195A (en) * | 1994-04-27 | 1995-11-07 | Du Pont Mitsui Polychem Co Ltd | Production of flexible polyvinyl chloride resin composition and production of flexible polyvinyl chloride composition molded product |
JP2006170343A (en) * | 2004-12-16 | 2006-06-29 | Mitsubishi Motors Corp | Automobile hose |
WO2013042764A1 (en) * | 2011-09-21 | 2013-03-28 | 日本ゼオン株式会社 | Nitrile copolymer rubber composition and rubber crosslink |
JP2017511758A (en) * | 2014-02-13 | 2017-04-27 | シーカ テクノロジー アクチェンゲゼルシャフト | Method for producing plasticized PVC semi-finished product |
JP2018052054A (en) * | 2016-09-30 | 2018-04-05 | 住友理工株式会社 | Hose manufacturing method |
Family Cites Families (1)
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---|---|---|---|---|
KR20140012125A (en) | 2011-03-31 | 2014-01-29 | 니타 가부시키가이샤 | Thermoplastic resin composition having high durability |
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59100152A (en) * | 1982-11-30 | 1984-06-09 | Toyoda Gosei Co Ltd | Vinyl chloride resin composition |
JPH06263924A (en) * | 1993-03-16 | 1994-09-20 | Nippon Zeon Co Ltd | Rubber composition |
JPH07292195A (en) * | 1994-04-27 | 1995-11-07 | Du Pont Mitsui Polychem Co Ltd | Production of flexible polyvinyl chloride resin composition and production of flexible polyvinyl chloride composition molded product |
JP2006170343A (en) * | 2004-12-16 | 2006-06-29 | Mitsubishi Motors Corp | Automobile hose |
WO2013042764A1 (en) * | 2011-09-21 | 2013-03-28 | 日本ゼオン株式会社 | Nitrile copolymer rubber composition and rubber crosslink |
JP2017511758A (en) * | 2014-02-13 | 2017-04-27 | シーカ テクノロジー アクチェンゲゼルシャフト | Method for producing plasticized PVC semi-finished product |
JP2018052054A (en) * | 2016-09-30 | 2018-04-05 | 住友理工株式会社 | Hose manufacturing method |
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